WO2022195041A1 - Stabilizer composition, use of the stabilizer composition, method for stabilizing condensation polymers against hydrolytic degradation, and hydrolysis-stabilized composition and molding or molded part consisting thereof - Google Patents

Stabilizer composition, use of the stabilizer composition, method for stabilizing condensation polymers against hydrolytic degradation, and hydrolysis-stabilized composition and molding or molded part consisting thereof Download PDF

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WO2022195041A1
WO2022195041A1 PCT/EP2022/057056 EP2022057056W WO2022195041A1 WO 2022195041 A1 WO2022195041 A1 WO 2022195041A1 EP 2022057056 W EP2022057056 W EP 2022057056W WO 2022195041 A1 WO2022195041 A1 WO 2022195041A1
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Prior art keywords
methyl
bis
aziridinecarboxamide
aziridinyl
acid
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PCT/EP2022/057056
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German (de)
French (fr)
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Jannik HALLSTEIN
Elke Metzsch-Zilligen
Rudolf Pfaendner
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Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
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Priority to EP22716213.8A priority Critical patent/EP4308642A1/en
Priority to CN202280022459.4A priority patent/CN117015566A/en
Priority to KR1020237035322A priority patent/KR20230158068A/en
Priority to US18/549,802 priority patent/US20240182683A1/en
Priority to JP2023553994A priority patent/JP2024510155A/en
Publication of WO2022195041A1 publication Critical patent/WO2022195041A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/34—Silicon-containing compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/38—Boron-containing compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C08L69/005—Polyester-carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K2003/343—Peroxyhydrates, peroxyacids or salts thereof

Definitions

  • Stabilizer composition use of the stabilizer composition, process for stabilizing condensation polymers against hydrolytic degradation, and hydrolysis-stabilized composition and molding or molding made therefrom
  • the present invention relates to a novel stabilizer composition based on an aziridine and at least one hydrotalcite, zeolite, dawsonite or mixtures thereof.
  • the stabilizer composition is suitable for stabilizing condensation polymers, in particular aliphatic polyesters, against hydrolytic degradation.
  • the invention also relates to the use of the stabilizer composition according to the invention and to a method for stabilizing condensation polymers against hydrolytic degradation.
  • the present invention relates to moldings and moldings that can be produced from the composition according to the invention.
  • Polycondensation polymers such as polyesters, polyamides and polycarbonates are generally classified as hydrolysis-sensitive polymers, since the chemical bonds of these polymers can be broken by water. This can be advantageous for degradation of these polymers, for example in the environment, but is also often a disadvantage, particularly in the case of technical applications and desired extended useful lives.
  • Polymers from fossil raw materials are increasingly being replaced by polymers from renewable raw materials.
  • These "bio" polymers are, for example, based on aliphatic polyesters such as polylactic acid, also referred to as polylactide or PLA.
  • aliphatic ester groups are significantly more sensitive to hydrolysis than (partly) aromatic ester groups (see, for example, M. Dröscher et al, Angewandte Makromolecular Chemistry 1984, 128, 203-213).
  • WO 2012 072 489 mentions carbodiimides, polycarbodiimides, epoxides, alkyl ketene dimers and oxazolidinones as hydrolysis stabilizers.
  • CN 101 759 969 describes hydrolysis-resistant PLA-based compositions which contain carbodiimides, epoxy, oxoazolines, oxazines or aziridines.
  • Compositions are also known, for example from WO 94/24201, which contain further additives such as calcium oxide or calcium silicates in addition to the hydrolysis stabilizer in the form of epoxides.
  • drilling fluids which can contain aziridines, hydrotalcites and degradable polymers (WO2015/065575).
  • Polycondensates containing aziridines are therefore to be regarded as the closest prior art.
  • aziridines in polyesters and PLA is mentioned in US 3959228, in TW 1472575, in US 2014/0100318 or US 2016/024297.
  • Patent claim 9 specifies possible uses of the stabilizer composition
  • patent claim 10 relates to a method for stabilizing condensation polymers against hydrolytic degradation
  • Patent claim 13 relates to a hydrolysis-stabilized composition
  • patent claim 17 to a molded part or a molded body that can be produced from the hydrolysis-stabilized composition.
  • the present invention thus relates to a stabilizer composition consisting of at least one aziridine and at least one hydrotalcite, zeolite, dawsonite or mixtures thereof.
  • polyesters with combinations of aziridines with hydrotalcites, zeolites or dawsonite have particularly good hydrolytic stability. These combinations have not previously been described in the literature.
  • New hydrolysis-stabilized plastic compositions made from polycondensation polymers such as polyesters or polyamides, as well as new stabilizer compositions for improving the hydrolytic stability with high effectiveness, particularly in the case of biopolymers such as PLA, are made available.
  • the at least one aziridine is selected from the group consisting of monofunctional, difunctional, tetrafunctional and/or multifunctional aziridines with, for example, the following structures:
  • 1-Aziridinepropionic acid 2-methyl-, 1,1'-[2-[[3-[3-(1-aziridinyl)-1-oxopropoxy]-2-(hydroxymethyl)-2-[[3-( 2-methyl-1-aziridinyl)-1-ox-opropoxy]methyl]propoxy]methyl]-2-[[3-(2-methyl-1-aziridinyl)-1-ox-opropoxy]methyl]-1,3 -propanediyl]ester;
  • Particularly suitable aziridines are:
  • Particularly preferred aziridines are the following compounds:
  • aziridines mentioned are commercially available, e.g. from Menadiona (Barcelona, Spain) or Polyaziridine LLC (Palm Beach, USA).
  • the at least one hydrotalcite is preferably selected from the group consisting of compounds of the general formula (M 2+ ) 1-x . (M 3+ ) x . (OH) 2 . (A n- ) x/n . m H 2 O where
  • A is an anion with the valence n, preferably OH-, HCO 3 -, CH 3 COO-, C 6 H 5 COO-, CO 3 2- , SO 4 2- , HPO 4 2- , n is 1 or 2,
  • m is a number from 0 to 20.
  • the hydrotalcites are selected from the group consisting of Ca 4 Al 2 (OH) 12 CO 3 • 5 H 2 O, Al 2 O 3 • 6 MgO • CO 2 • 12 H 2 O, Mg 4.5 Al 2 (OH ) 13 • CO 3 • 3.5 H 2 O, Mg 6 AI 2 (OH) 16 • CO 3 • 4 H 2 O, 4 MgO • AIO3 • CO 2 • 9 H 2 O, 4 MgO • AI 2 O 3 • CO 2 • 6 H 2 O, ZnO • 3 MgO • Al 2 O 3 • CO 2 • 8-9 H 2 O and ZnO • 3 MgO • Al 2 O 3 • CO 2 • 5-6 H 2 O.
  • the at least one dawsonite is selected from the group consisting of compounds of the general formula whereby
  • M an element selected from the group consisting of H, Li, Na, K, Mg 1/2 , Ca 1/2 , Sr 1/2 , Zn 1/2 ;
  • Z is a substituent selected from the group consisting of CO2, SO2, (Cl 2 O 7 ) 1/2 , B 4 O 6 , S 2 O 2 (thiosulfate) and/or C 2 O 2 (oxalate); m if M is Mg 1/2 , Ca 1/2 , a number between 1 and 2, in all other cases a number between 1 and 3; n is a number between 1 and 4; o a number between 2 and 4; and p is a number between 0 and 30.
  • the at least one dawsonite is selected from the group consisting of potassium aluminocarbonate sodium aluminothiosulphate potassium alumosulfite Calcium alumooxalate ⁇ (CaO) (Al 2 O 3 ) (C 2 O 2 ) 2 .5H 2 O ⁇ , magnesium alumotet- .aborate ⁇ (MgO)-(AI 2 O 3 ) ⁇ (B 4 O 6 ) 2 ⁇ 5 H 2 O ⁇ , sodium alumodihydroxycarbonate, potassium alumodihydroxycarbonate and naturally occurring alkali alumocarbonate minerals such as indigirite, tunisit, alumohydrocalcite and Strontiodresserit.
  • potassium aluminocarbonate sodium aluminothiosulphate potassium alumosulfite Calcium alumooxalate ⁇ (CaO) (Al 2 O 3 ) (C 2 O 2 ) 2 .5H 2 O ⁇ magnesium al
  • the at least one zeolite is preferably selected from the group consisting of compounds of the general formula
  • M an element of the first or second main group, in particular Li, Na, K, Mg, Ca, Sr or Ba; y:x has a value from 0.8 to 15, preferably from 0.8 to 1.2, and w is a number from 0 to 300, preferably from 0.5 to 5.
  • hydrotalcites, zeolites, dawsonites or mixtures thereof are used as an anhydrous formulation.
  • the weight ratio of the total of the aziridine to all of the at least one hydrotalcite, dawsonite and/or zeolite is from 20:1 to 1:20, preferably from 10:1 to 1:10, particularly preferably from 5:1 to 1:5.
  • the present invention relates to the use of a stabilizer composition according to the invention as described above for stabilizing condensation polymers against hydrolytic degradation.
  • the present invention relates to a process for stabilizing condensation polymers against hydrolytic degradation, in which a stabilizer composition according to the invention, described above, is admixed to or blended with the condensation polymer.
  • the stabilizer composition is present in a weight ratio of from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight. %, particularly preferably from 0.1 to 3% by weight, based on the polycondensation polymer, is used or mixed in.
  • the present invention relates to a hydrolysis-stabilized composition containing or consisting of at least one condensation polymer and a stabilizer composition according to the invention according to any one of claims 1 to 8.
  • the condensation polymer is selected from the group consisting of a) polyamides, such as polyamide-6, 6.6, 6.9, 6.10, 4.6, 4.10, 6.12, 10.10 , 10.12, 12.12, polyamide 4, polyamide 7, polyamide 8, polyamide 9, polyamide 11, polyamide 12 and (partly) aromatic polyamides such as polyphthalamides, for example produced from terephthalic acid and/or isophthalic acid and aliphatic diamines such as hexamethylenediamine or m-xylylenediamine or from aliphatic dicarboxylic acids such as adipic acid o- of sebacic acid and aromatic diamines such as 1,4- or 1,3-diaminobenzene, referred to, for example, as polyamide 6T, polyamide 9T, polyamide 61, polyamide 6-3-T, blends of different polyamides such as PA-6 and PA 6.6, PA6T and PA6I, PA-6.6
  • polyesters made from aliphatic or aromatic dicarboxylic acids and diols or from hydroxycarboxylic acids in particular aliphatic polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polypropylene terephthalate (PPT), polyethylene naphthylate (PEN) , poly-1,4-dimethylol-cyclohexane terephthalate, polyhydroxybenzoate, polyhydroxynaphthalate, polylactic acid (PLA), polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polyethylene succinate cinate, polycaprolactone, c) polycarbonates, polyester carbonates, and blends such as PC/ABS, PC/PBT, PC/PET/PBT, PC/PA, d) and mixtures, combinations or blends of
  • polymers specified under a) to c) can have both amorphous and (partially) crystalline morphologies.
  • polyesters are aliphatic polyesters, i. H. Polyester which can be produced from aliphatic dicarboxylic acids and aliphatic diols or from aliphatic lactones.
  • diols for aliphatic polyesters examples include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, 3 -Methyl-2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol , -1,6,2-ethylhexanediol-1,3, 2,2-diethylpropanediol-1,3, 2,2-bis(4-hydroxycyclohexyl)propane, 2,2-bis(4-hydroxypropoxyphenyl
  • dicarboxylic acids examples include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, hexadecanedioic acid, cyclohexane-1,3-dicarboxylic acid or cyclohexane-1,4-dicarboxylic acid.
  • aromatic structures can also be present to a minor extent, up to 20 mol %, preferably less than 10 mol %, very particularly preferably less than 1 mol %.
  • Suitable aromatic structures are hydroquinone, resorcinol, 2,6-naphthalenediol, 1,8-naphthalenediol, bisphenol-A in the case of diols, and terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid in the case of dicarboxylic acids, an example of a heterocyclic aromatic dicarboxylic acid is 2,5-furandicarboxylic acid.
  • Suitable hydroxycarboxylic acids are, for example, lactic acid, glycolic acid, 4-hydroxybutyric acid, 3-hydroxybutyric acid or 3-hydroxyvaleric acid, and a hydroxycarboxylic acid with aromatic components is mandelic acid.
  • polyesters are, in particular, polybutylene terephthalate (PBT) and copolymers of 1,4-butanediol with terephthalic acid, adipic acid or sebacic acid.
  • PBT polybutylene terephthalate
  • copolymers of 1,4-butanediol with terephthalic acid, adipic acid or sebacic acid are preferred polyesters.
  • Preferred polyamides are in particular polyamide 6, polyamide 6.6, blends of polyamide 6 with polyamide 6.6, polyamide 10.10, polyamide 10.12, polyamide 12.12, polyamide 11 and polyamide 12.
  • compositions can contain other additives selected from the group consisting of secondary antioxidants, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact modifiers, plasticizers, lubricants, rheology modifiers , thixotropic agents, chain extenders, processing aids, additives, flame retardants, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anticrosslinking agents, hydrophilizing agents, hydrophobing agents, hydrolysis stabilizers, adhesion promoters, dispersing agents, compatibilizers, oxygen scavengers, acid scavengers, Blowing agents, degradation additives, defoaming aids, odor traps, marking agents, antifogging agents, fillers and reinforcing materials are used.
  • additives selected from the group consisting of secondary antioxidants, UV absorbers, light stabilizer
  • compositions contain, in particular, phosphites or phosphonites, fillers or acid scavengers.
  • Suitable phenolic antioxidants are:
  • Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di -tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methyl-phenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethylphenol , 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethyl- phenol, linear or branched nonylphenols such as 2,6-dinonyl- 4-methyl-phenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl-6-(
  • alkylthiomethyl phenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol;
  • Hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methyloxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4 -octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl -4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxylphenyl)adipate;
  • Tocopherols such as ⁇ -, ⁇ -, ⁇ -, ⁇ -tocopherol and mixtures of these (vitamin E); Hydroxylated thiodiphenyl ethers such as 2,2'-thiobis(6-tert-butyl-4-methyl-phenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl- 3-methyl- phenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-di-secamylphenol), 4,4'-bis( 2,6-dimethyl-4-hydroxyphenyl) disulfide;
  • Hydroxylated thiodiphenyl ethers such as 2,2'-thiobis(6-tert-butyl-4-methyl-phenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl- 3-
  • Alkylidenebisphenols such as 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl- 6-( ⁇ -methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4 ,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2, 2'-methylenebis[6-(a-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-( ⁇ , ⁇ -dimethylbenzyl)-4-nonyl
  • O-, N- and S-benzyl compounds such as 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate , tridecyl 4-hydroxy-3,5-di-tert-butyl-benzyl-mercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy -2,6-dimethyl-benzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate;
  • Hydroxybenzylated malonates such as dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methyl-benzyl) malonate, didodecylmercaptoethyl 2,2-bis(3,5-di-tert-butyl-4-hydroxy-benzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2- bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate; Aromatic hydroxybenzyl compounds such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert- butyl-4-hydroxy-benzyl)-2,3,5,6-te
  • Triazine compounds such as 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3 ,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxy-phenoxy) -1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3, 5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(
  • Benzyl phosphonates such as dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl
  • acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate;
  • Esters of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols e.g. methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol , 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2
  • Esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols for example methanol, ethanol, n-octanol, i-octanol, octade- canol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl )oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]oc
  • Esters of ⁇ -(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2- Propanediol, Neopentyl Glycol, Thiodiethylene Glycol, Diethylene Glycol, Triethylene Glycol, Pentaerythritol, Tris-(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-
  • Esters of (3,5-di-tert-butyl-4-hydroxyphenyl)acetic acid with monohydric or polyhydric alcohols e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;
  • Amides of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid such as N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N' - Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'- Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-
  • vitamin C Ascorbic acid (vitamin C).
  • Particularly preferred phenolic antioxidants are the following structures:
  • n is an integer and is between 2 and 10.
  • phenolic antioxidants are based on renewable raw materials phenolic antioxidants such.
  • chrysin quercitin, hesperidin, neohesperidin, naringin, Morin, kaempferol, fisetin, datiscetin, luteolin, apigenin, taxifolin, isoflavones such as genistein, genistin, daidzein, daidzin, formononetin, anthocyanins such as delphinidin and malvidin, curcumin, carnosic acid, carnosol, rosmarinic acid, tannin and resveratrol and carotenoids with alcoholic groups, such as beta-cryptoxanthin, lutein, zeaxanthin or astaxanthin.
  • alcoholic groups such as beta-cryptoxanthin, lutein, zeaxanthin or astaxanthin.
  • Suitable aminic antioxidants are:
  • Preferred amine antioxidants are: N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p -phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p- phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3 -dimethylbutyl)-N'-phenyl-p-
  • Particularly preferred aminic antioxidants are the structures:
  • Preferred hydroxylamines or N-oxides are, for example, N,N-dialkylhydroxylamine, N,N-dibenzylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-distearylhydroxylamine, N-benzyl- ⁇ -phenylnitrone, N- Octadecyl-a-hexadecylnitrone, as well as Genox EP (SI Group) according to the formula:
  • Suitable lactones are benzofuranones and indolinones such as 3-(4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl- 3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-(2-hydroxyethoxy)phenyl)benzofuran-2 -one), 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl -benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofur
  • Preferred fillers are calcium carbonate, silicates, talc, mica, kaolin, metal oxides and metal hydroxides, carbon black, graphite, wood flour or fibers from natural products such as cellulose.
  • Other suitable fillers are hydrotalcites or zeolites or phyllosilicates such as montmorillonite, bentonite, beidelite, mica, hectorite, saponite, vermiculite, ledikite, magadite, illite, kaolinite, wollastonite, attapulgite.
  • Suitable secondary antioxidants are in particular phosphites or phosphonites such as e.g.
  • Triphenyl phosphite diphenylalkyl phosphites, phenyldialkyl phosphites, tri(nonylphenyl) phosphite, trilauryl phosphites, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis(2,4-di-tert -butylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxy
  • Particularly preferred phosphites are:
  • a preferred phosphonite is:
  • Suitable secondary antioxidants are also organo-sulphur compounds such as sulfides and disulfides, for example distearyl thiodipropionate, dilauryl thiodipropionate, ditridecyldithiopropionate, ditetradecyl thiodipropionate, 3-(dodecylthio)-, 1,1'-[2,2-bis[[3-(dodecylthio). )-1-oxopropoxy]methyl]-1,3-propanediyl]propanoic acid ester.
  • organo-sulphur compounds such as sulfides and disulfides, for example distearyl thiodipropionate, dilauryl thiodipropionate, ditridecyldithiopropionate, ditetradecyl thiodipropionate, 3-(dodecylthio)-, 1,1'-[2,2-bis[
  • Suitable acid scavengers are salts of mono, di, tri or tetravalent metals, preferably alkali metals, alkaline earth metals, aluminum or zinc, formed in particular with fatty acids, such as calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, calcium laurate, Calcium behenate, calcium lactate, calcium stearoyl-2-lactate
  • Suitable acid scavengers are hydrotalcites, in particular synthetic hydrotalcites based on aluminium, magnesium and zinc, hydrocalumites, zeolites, alkaline earth metal oxides, in particular calcium oxide and magnesium oxide as well as zinc oxide, alkaline earth metal carbonates, in particular calcium carbonate, magnesium carbonate and dolomite, and hydroxides, in particular brucite (magnesium hydroxide),
  • Suitable co-stabilizers are also polyols, in particular alditols or cyclitols.
  • Polyols are, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, short-chain polyether polyols or polyester polyols, as well as hyperbranched polymers/oligomers or dendrimers with alcohol groups, for example
  • the at least one alditol is preferably selected from the group consisting of threitol, erythritol, galactitol, mannitol, ribitol, sorbitol, xylitol, arabitol, isomalt, lactitol, maltitol, altritol, iditol, maltotritol and hydrogenated oligo- and polysaccharides with polyol - end groups and mixtures thereof.
  • the at least one preferred alditol is particularly preferably selected from the group consisting of erythritol, mannitol, isomalt, maltitol and mixtures thereof.
  • heptitols and octitols meso-glycero-allo-heptitol, D-glycero-D-altro-heptitol, D-glycero-D-manno-heptitol, meso-glycero-gulo-heptitol, D-glycero- D-galacto-heptitol (perseitol), D-glycero-D-gluco-heptitol, L-glycero-D-gluco-heptitol, D-erythro-L-galacto-octitol, D-threo-L-galacto-octitol.
  • the at least one cyclitol may be selected from the group consisting of inositol (myo, scyllo-, D-chiro-, L-chiro-, muco-, neo-, allo-, epi- and cis-inositol), 1,2 ,3,4-tetrahydroxycyclohexane, 1,2,3,4,5-pentahydroxycyclohexane, Quercitol, Viscumitol, Bornesitol, Conduritol, Ononitol, Pinitol, Pinpollitol, quebrachitol, ciceritol, quinic acid, shikimic acid and valienol, preference being given to myo-inositol (myo-inositol).
  • inositol myo, scyllo-, D-chiro-, L-chiro-, muco-, neo-, allo-, epi- and cis-i
  • Suitable light stabilizers are compounds based on 2-(2'-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, esters of benzoic acids, acrylates, oxamides and 2-(2-hydroxyphenyl)-1,3,5-triazines.
  • 2-(2'-hydroxyphenyl)benzotriazoles examples include 2-(2'-hydroxy-5'methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole , 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3 ',5'-Di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl-5-chlorobenzotriazole, 2-( 3'-sec-butyl-5'-tert-butyl-2'-hydroxy-phenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazo
  • 2-hydroxybenzophenones 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy -4,4'-dimethyloxy derivatives of 2-hydroxybenzophenones.
  • Suitable acrylates are ethyl ⁇ -cyano- ⁇ , ⁇ -diphenyl acrylate, isooctyl ⁇ -cyano- ⁇ , ⁇ -diphenyl acrylate, methyl ⁇ -carbomethoxycinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, butyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, methyl ⁇ -carbomethoxy-p-methoxycinnamate and N-( ⁇ -carbo-methoxy- ⁇ -cyanovinyl)-2-methylindoline.
  • esters of benzoic acids are 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl-3,5-di-tert- butyl 4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxy-benzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6- di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • Suitable oxamides are 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'- di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixtures with 2- ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
  • 2-(2-hydroxyphenyl)-1,3,5-triazines examples include 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy- 4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy -4-octyloxyphenyl)-4,6-bis(4-methyl- phenyl-1,3,5-triazine, 2-(2-Hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethyl- phenyl)-1,
  • suitable metal deactivators are N,N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4- hydroxy-phenyl-propionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacoylbis- phenylhydrazide, N,N'-diacetyladipoyldihydrazide, N,N'-bis(salicyloyl) oxylyldihydrazide, N,N'-bis(salicyloyl)thiopropionyldihydrazide.
  • metal deactivators are:
  • Suitable low molecular weight hindered amines are 1,1-bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebazate, bis( 1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebazate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-n-butyl-3,5-di-tert -butyl-4-hydroxy-benzylmalonate, the condensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N,N'-bis( 2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(
  • the structures given above also include the sterically hindered N-H, N-alkyl such as N-methyl or N-octyl, the N-alkoxy derivatives such as N-methoxy or N-octyloxy, the cycloalkyl derivatives such as N -cyclohexyloxy and the N-(2-hydroxy-2-methylpropoxy) analogs.
  • Preferred low molecular weight hindered amines also have the following structures:
  • Preferred oligomeric or polymeric hindered amines are:
  • n is in each case from 3 to 100.
  • Another suitable light stabilizer is Hostanox NOW (manufacturer: Clariant SE) with the following general structure: where R is -OC(O)-C 15 H 31 or -OC(O)-C 17 H 35 .
  • the structures given above also include the sterically hindered NH, N-alkyl such as N-methyl or N-octyl, the N-alkoxy derivatives such as N-methoxy or N-octyloxy, the cycloalkyl derivatives such as N -cyclohexyloxy and the N-(2-hydroxy-2-methylpropoxy) analogs.
  • Suitable dispersing agents are:
  • Polyacrylates e.g., copolymers with long-chain side groups, polyacrylate block copolymers, alkylamides: e.g., N,N'-1,2-ethanediylbisoctadecanamide sorbitan esters, e.g., monostearyl sorbitan esters, titanates and zirconates, reactive copolymers with functional groups, e.g., polypropylene-co-acrylic acid, Polypropylene-co-maleic anhydride, polyethylene-co-glycidyl methacrylate, polystyrene-alt-maleic anhydride-polysiloxanes: e.g.
  • dimethylsilanediol-ethylene oxide copolymer polyphenylsiloxane copolymer, amphiphilic copolymers: e.g. polyethylene block polyethylene oxide, dendrimers, e.g. den - drimmer.
  • Suitable antinucleating agents are azine dyes such as nigrosine.
  • Suitable flame retardants are in particular a) Inorganic flame retardants such as Al(OH) 3 , Mg(OH) 2 , AlO(OH), MgCO 3 , phyllosilicates such as montmorillonite or sepiolite, unmodified or organically modified, double salts such as Mg-Al- Silicates, POSS (polyhedral oligomeric silsesquioxane) compounds, huntite, hydromagnesite or halloysite as well as Sb 2 O 3 , Sb 2 O 5 , MoO 3 , zinc stannate, zinc hydroxystannate, b) nitrogen-containing flame retardants such as melamine, melem, Melam, melon, melamine derivatives, melamine condensation products or melamine salts, benzoguanamine, polyisocyanurate, allantoin, phosphacene, in particular melamine cyanurate, melamine phosphate, dimelamin phosphate,
  • plasticizers examples include phthalic acid esters, adipic acid esters, citric acid esters, 1,2-cyclohexanedicarboxylic acid esters, trimellitic acid esters, isosorbide esters, phosphate esters, epoxides such as epoxidized soybean oil or aliphatic polyesters.
  • Suitable lubricants and processing aids are, for example, polyethylene waxes, polypropylene waxes, salts of fatty acids such as calcium stearate, zinc stearate or salts of montan waxes, amide waxes such as erucic acid amide or oleic acid amides, fluoropolymers, silicones or neoalkoxy titanate and zirconates.
  • Suitable pigments can be inorganic or organic in nature.
  • Inorganic pigments are, for example, titanium dioxide, zinc oxide, zinc sulfide, iron oxide, ultramarine, carbon black, organic pigments are, for example, anthraquinones, anthanthrones, benzimidazolones, quinacridones, diketopyrrolopyrroles, dioxazines, indanthrones, isoindolinones, azo compounds, perylenes, phthalocyanines nine or pyranthrones.
  • Other suitable pigments are metal-based effect pigments or metal-oxide-based pearlescent pigments.
  • Suitable optical brighteners are, for example, bisbenzoxazoles, phenylcoumarins or bis(styryl)biphenyls and in particular optical brighteners of the formulas:
  • Suitable filler deactivators are, for example, polysiloxanes, polyacrylates, in particular block copolymers such as polymethacrylic acid-polyalkylene oxide or polyglycidyl (meth)acrylates and their copolymers, for example with styrene, and epoxides, for example of the following structures:
  • Suitable antistatic agents are ethoxylated alkylamines, fatty acid esters, alkylsulfonates and polymers such as polyetheramides.
  • Suitable antiozonants are the amines mentioned above, such as N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl) -p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenedi- min, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl -p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine.
  • Suitable nucleating agents are talc, alkali metal or alkaline earth metal salts of mono- and polyfunctional carboxylic acids such as. benzoic acid, succinic acid, adipic acid, e.g ) phosphate, as well as trisamides and diamides such as e.g. propanamide) or 2,6-naphthalene dicarboxylic acid dicyclohexylamide.
  • Suitable additives for increasing the molecular weight of polycondensation polymers are diepoxides, bis-oxazolines, bis-oxazolones, bis-oxazines, diisocyanates, dianhydrides, bis-acyllactams, bis-maleimides, dicyanates, carbodiimides.
  • chain extenders are polymeric compounds such as, for example, polystyrene-polyacrylate-polyglycidyl (meth)acrylate copolymers, polystyrene-maleic anhydride copolymers and polyethylene-maleic anhydride copolymers.
  • Suitable additives for increasing the electrical conductivity are, for example, the antistatic agents mentioned, soot and carbon compounds such as carbon nanotubes and graphene, metal powder such as copper powder and conductive polymers such as polypyrroles, polyanilines and polythiophenes.
  • suitable additives for increasing the thermal conductivity are aluminum nitrides and boron nitrides.
  • suitable infrared-active additives are aluminum silicates, hydrotalcites or dyes such as phthalocyanines or anthraquinones.
  • suitable mold release agents are silicones, soaps and waxes such as montan waxes.
  • the additive composition described above and any additional additives are incorporated into the plastic using conventional processing methods, with the polymer being melted and mixed with the additive composition according to the invention and any other additives, preferably using mixers, kneaders or extruders.
  • Preferred processing machines are extruders such as, for example, single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, co-kneaders, which are preferably equipped with vacuum degassing.
  • the processing can take place under air or possibly under inert gas conditions.
  • additive compositions according to the invention can be produced and introduced in the form of so-called masterbatches or concentrates, which contain, for example, 10-90% of the compositions according to the invention in a polymer.
  • the present invention relates to a molded part or a molded body that can be produced from a hydrolysis-stabilized composition according to the present invention.
  • the molded part or molded body is selected from the group consisting of foils, films, foams, fibers, cables and pipes, profiles, hollow bodies, ribbons, membranes such as geomembranes, or adhesives, which are produced via extrusion, injection molding , blow molding, calendering, pressing processes, spinning processes, rotomoulding, e.g. for the electrical and electronics industry, construction industry, transport industry (car, plane, ship, train), for medical applications, for household and electrical appliances, vehicle parts, consumer goods , packaging, furniture, textiles.
  • Hydrotalcite 1 Actilox CAH EXP 0213; Supplier: Nabaltec Hydrotalcite 2: DHT-4C; Supplier: Kisuma Chemicals, calcined version of
  • Hydrotalcite 3 Hycite 713; Supplier: Clariant SE
  • Hydrotalcite 4 Sorbacid 911; Supplier: Clariant SE
  • Hydrotalcite 5 DHT-4A; Supplier: Kisuma Chemicals
  • AlfaAesar type 13X molecular sieve was used as the zeolite.
  • the aziridine is the POLY-U Powder from the manufacturer Menadiona.
  • the chemical name is N,N'-(methylenedi-p-phenylene)bis(aziridine-1-carboxamide).
  • a polylactide (PLA) (Luminy L130, supplier: Total Corbion) was tested together with the additives specified in Table 1 at a maximum of 200° C. in a twin-screw extruder (Process 11, manufacturer ThermoScientific) at a throughput of 800 g/h.
  • Polymer and additives were dried overnight in a vacuum dryer before processing. After compounding, the compounds were aged in deionized water at 60 °C in a heating cabinet for 2 weeks (336 hours). After aging, the samples were dried overnight and the MVR determined (190 °C / 2.16 kg).
  • a polybutylene terephthalate (PBT) (Pocan B1204, supplier: Lanxess) was extruded together with the additives specified in Table 2 at a maximum of 245° C. in a twin-screw extruder (Process 11, manufacturer ThermoScientific) at a throughput of 800 g/h.
  • Polymer and additives were dried overnight in a vacuum dryer before processing. After compounding, the compounds were aged at 85°C in an oven for 2 weeks (336 hours) in deionized water. After aging, the samples were dried overnight and the MVR was determined (250 °C / 2.16 kg).
  • a polyamide 6 (PA6) (Ultramid B27E, supplier: BASF) was combined with the additives specified in Table 3 at a maximum of 245° C. in a microcompounder (Micro 5cc Twin Screw Extruder, manufacturer DSM) compounded. Polymer and additives were dried overnight in a vacuum dryer before processing. After compounding, the compounds were aged at 85°C in an oven for 2 weeks (336 hours) in deionized water. After aging, the samples were dried overnight and the molecular weight determined by GPC.
  • PA6 Ultramid B27E, supplier: BASF
  • the MVR is a measure of the molecular weight of the polymer. The higher the MVR, the lower the molecular weight and thus the degradation of the polymer by hydrolysis that has taken place. The lower the MVR increase, the higher the hydrolytic stability. The combinations according to the invention therefore exhibit excellent hydrolytic stability.

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Abstract

The present invention relates to a new stabilizer composition on the basis of an aziridine and at least a hydrotalcite, zeolite, dawsonite or mixtures thereof. The stabilizer composition is suitable for stabilizing condensation polymers, in particular aliphatic polyesters against hydrolytic degradation. The invention also relates to the use of the stabilizer composition according to the invention and to a method for stabilizing condensation polymers against hydrolytic degradation. The present invention further relates to molded parts and moldings that can be produced from the composition according to the invention.

Description

Stabilisator-Zusammensetzung, Verwendung der Stabilisator-Zusammenset- zung, Verfahren zur Stabilisierung von Kondensationspolymeren gegen hydro- lytischen Abbau sowie hydrolysestabilisierte Zusammensetzung und Formkör- per oder Formteil hieraus Stabilizer composition, use of the stabilizer composition, process for stabilizing condensation polymers against hydrolytic degradation, and hydrolysis-stabilized composition and molding or molding made therefrom
Die vorliegende Erfindung betrifft eine neuartige Stabilisator-Zusammenset- zung, basierend auf einem Aziridin sowie mindestens einem Hydrotalcit, Zeo- lith, Dawsonit oder Mischungen hieraus. Die Stabilisator-Zusammensetzung eignet sich zur Stabilisierung von Kondensationspolymeren, insbesondere von aliphatischen Polyestern gegen hydrolytischen Abbau. Die Erfindung betrifft ebenso die Verwendung der erfindungsgemäßen Stabilisator-Zusammenset- zung sowie ein Verfahren zur Stabilisierung von Kondensationspolymeren ge- gen hydrolytischen Abbau. Des Weiteren betrifft die vorliegende Erfindung Formteile und Formkörper, die aus der erfindungsgemäßen Zusammensetzung herstellbar sind. The present invention relates to a novel stabilizer composition based on an aziridine and at least one hydrotalcite, zeolite, dawsonite or mixtures thereof. The stabilizer composition is suitable for stabilizing condensation polymers, in particular aliphatic polyesters, against hydrolytic degradation. The invention also relates to the use of the stabilizer composition according to the invention and to a method for stabilizing condensation polymers against hydrolytic degradation. Furthermore, the present invention relates to moldings and moldings that can be produced from the composition according to the invention.
Polykondensationspolymere wie Polyester, Polyamide und Polycarbonate sind grundsätzlich als hydrolyseempfindliche Polymere einzustufen, da die chemi- schen Bindungen dieser Polymeren durch Wasser gespalten werden können. Dies kann für einen Abbau dieser Polymeren z.B. in der Umwelt vorteilhaft sein, ist jedoch auch häufig von Nachteil insbesondere bei technischen Einsatzzwe- cken und erwünschten ausgedehnten Nutzungsdauern. In zunehmendem Maße werden Polymere aus fossilen Rohstoffen durch Polymere aus nachwach- senden Rohstoffen ersetzt. Diese „Bio"-Polymeren sind beispielsweise auf der Basis von aliphatischen Polyestern wie z.B. Polymilchsäure auch als Polylactid oder PLA bezeichnet. Aliphatische Estergruppierungen sind jedoch deutlich hydrolyseempfindlicher als (teil-)aromatische Estergruppen (s. z.B. M. Dröscher et al, Angewandte Makromolekulare Chemie 1984, 128, 203-213). Polycondensation polymers such as polyesters, polyamides and polycarbonates are generally classified as hydrolysis-sensitive polymers, since the chemical bonds of these polymers can be broken by water. This can be advantageous for degradation of these polymers, for example in the environment, but is also often a disadvantage, particularly in the case of technical applications and desired extended useful lives. Polymers from fossil raw materials are increasingly being replaced by polymers from renewable raw materials. These "bio" polymers are, for example, based on aliphatic polyesters such as polylactic acid, also referred to as polylactide or PLA. However, aliphatic ester groups are significantly more sensitive to hydrolysis than (partly) aromatic ester groups (see, for example, M. Dröscher et al, Angewandte Makromolecular Chemistry 1984, 128, 203-213).
Eine Verbesserung der Hydrolysestabilität von Polykondensationspolymeren und von PLA ist eine bekannte Fragestellung. Zum Beispiel werden in WO 2012 072 489 als Hydrolysestabilisatoren Carbodiimide, Polycarbodiimide, Epoxide, Alkylketendimere und Oxazolidinone genannt. In CN 101 759 969 werden hyd- rolysebeständige PLA basierende Zusammensetzungen beschrieben, die Car- bodiimide, Epoxy, Oxoazoline, Oxazine oder Aziridine enthalten. Es sind eben- falls z.B. aus WO 94/24201 Zusammensetzungen bekannt, die neben dem Hyd- rolysestabilisator in Form von Epoxiden weitere Zusätze wie Calciumoxid oder Calciumsilikate enthalten. Die Verwendung von Aziridinen in Polyestern und PLA wird weiterhin beispielsweise in US 3 959 228, in TW 1472575 oder in US 2014/0100318 erwähnt. Durch bestimmte Zusätze wie z.B. Füllstoffe kann je- doch auch die Hydrolysebeständigkeit negativ beeinflusst werden, so ist z.B. bekannt, dass Schichtsilikate wie Montmorillonite die Hydrolyse von PLA be- schleunigen (A. Rapacz-Kmita et al. Materials Letters 2015, 146, 73-76, Q. Zhao et al. Polymer Degradation and Stability 2008, 93, 1450-1459). Improving the hydrolytic stability of polycondensation polymers and PLA is a well-known issue. For example, WO 2012 072 489 mentions carbodiimides, polycarbodiimides, epoxides, alkyl ketene dimers and oxazolidinones as hydrolysis stabilizers. CN 101 759 969 describes hydrolysis-resistant PLA-based compositions which contain carbodiimides, epoxy, oxoazolines, oxazines or aziridines. Compositions are also known, for example from WO 94/24201, which contain further additives such as calcium oxide or calcium silicates in addition to the hydrolysis stabilizer in the form of epoxides. The use of aziridines in polyesters and PLA is also mentioned, for example, in US Pat. No. 3,959,228, in TW 1472575 or in US 2014/0100318. However, certain additives such as fillers can also have a negative impact on the hydrolysis resistance, for example it is known that phyllosilicates such as montmorillonite accelerate the hydrolysis of PLA (A. Rapacz-Kmita et al. Materials Letters 2015, 146, 73- 76, Q Zhao et al Polymer Degradation and Stability 2008, 93, 1450-1459).
Zudem sind Bohrflüssigkeiten bekannt, die Aziridine, Hydrotalcite und abbau- bare Polymere enthalten können (WO2015/065575). In addition, drilling fluids are known which can contain aziridines, hydrotalcites and degradable polymers (WO2015/065575).
Als nächster Stand derTechnik sind daher Polykondensate anzusehen, die Aziri- dine enthalten. Beispielsweise wird die Verwendung von Aziridinen in Polyes- tern und PLA in US 3959228, in TW 1472575, in US 2014/0100318 oder US 2016/024297 erwähnt. Polycondensates containing aziridines are therefore to be regarded as the closest prior art. For example, the use of aziridines in polyesters and PLA is mentioned in US 3959228, in TW 1472575, in US 2014/0100318 or US 2016/024297.
Es besteht daher der Bedarf, die Hydrolysestabilität von Polykondensationspo- lymeren, insbesondere von Polyestern und vor allem von aliphatischen Polyes- tern wie PLA zu erhöhen, um die Einsatzmöglichkeiten dieser Polymeren zu er- weitern. There is therefore a need to determine the hydrolytic stability of polycondensation lymers, in particular of polyesters and above all of aliphatic polyesters such as PLA, in order to expand the possible uses of these polymers.
Diese Aufgabe wird hinsichtlich einer Stabilisator-Zusammensetzung mit den Merkmalen des Patentanspruchs 1 gelöst. Mit Patentanspruch 9 werden Ver- wendungsmöglichkeiten der Stabilisator-Zusammensetzung angegeben, wäh- rend Patentanspruch 10 ein Verfahren zur Stabilisierung von Kondensationspo- lymeren gegen hydrolytischen Abbau betrifft. Patentanspruch 13 betrifft eine hydrolysestabilisierte Zusammensetzung, Patentanspruch 17 ein Formteil oder einen Formkörper, herstellbar aus der hydrolysestabilisierten Zusammenset- zung. This object is achieved with the features of claim 1 with regard to a stabilizer composition. Patent claim 9 specifies possible uses of the stabilizer composition, while patent claim 10 relates to a method for stabilizing condensation polymers against hydrolytic degradation. Patent claim 13 relates to a hydrolysis-stabilized composition, patent claim 17 to a molded part or a molded body that can be produced from the hydrolysis-stabilized composition.
Die abhängigen Patentansprüche betreffen dabei jeweils vorteilhafte Weiter- bildungen. The dependent patent claims each relate to advantageous developments.
Gemäß einem ersten Aspekt betrifft die vorliegende Erfindung somit eine Sta- bilisator-Zusammensetzung, bestehend aus mindestens einem Aziridin und mindestens einem Hydrotalcit, Zeolith, Dawsonit oder Mischungen hieraus.According to a first aspect, the present invention thus relates to a stabilizer composition consisting of at least one aziridine and at least one hydrotalcite, zeolite, dawsonite or mixtures thereof.
Es ist als überraschend anzusehen, dass Polyester mit Kombinationen von Aziri- dinen mit Hydrotalciten, Zeolithen oder Dawsoniten eine besonders gute Hyd- rolysestabilität aufweisen. Diese Kombinationen sind in der Literatur bisher nicht beschrieben. It is surprising that polyesters with combinations of aziridines with hydrotalcites, zeolites or dawsonite have particularly good hydrolytic stability. These combinations have not previously been described in the literature.
Es werden neue hydrolysestabilisierte Kunststoffzusammensetzungen aus Po- lykondensationspolymeren wie Polyester oder Polyamide, sowie neue Stabi- lisatorzusammensetzungen zur Verbesserung der Hydrolysestabilität mit hoher Wirksamkeit, insbesondere bei Biopolymeren wie PLA zur Verfügung gestellt. New hydrolysis-stabilized plastic compositions made from polycondensation polymers such as polyesters or polyamides, as well as new stabilizer compositions for improving the hydrolytic stability with high effectiveness, particularly in the case of biopolymers such as PLA, are made available.
Gemäß einer bevorzugten Ausführungsform ist das mindestens ein Aziridin aus- gewählt aus der Gruppe bestehend aus monofunktionellen, difunktioinellen, tetrafunktionellen und/oder multifunktionallen Aziridinen mit beispielsweise den folgenden Strukturen: According to a preferred embodiment, the at least one aziridine is selected from the group consisting of monofunctional, difunctional, tetrafunctional and/or multifunctional aziridines with, for example, the following structures:
A) Monofunktionellen Aziridinen 1 -Aziridincarboxamid, N-octadecyl-; A) Monofunctional aziridines 1 -aziridinecarboxamide, N-octadecyl-;
1-Aziridincarboxamid, N-phenyl-; 1-aziridinecarboxamide, N-phenyl-;
1 -Aziridincarboxamid, N-cyclohexyl-; 1 -aziridinecarboxamide, N -cyclohexyl-;
1-Aziridincarboxamid, N-1-naphthalenyl-; 1-aziridinecarboxamide, N-1-naphthalenyl-;
1-Aziridincarboxamid, N-decyl-; 1-aziridinecarboxamide, N-decyl-;
N-Benzyloxycarbonylaziridine; N-benzyloxycarbonylaziridines;
(4-Methoxyphenyl)(2-methyl-1-aziridinyl)methanone; (4-Methoxyphenyl)(2-methyl-1-aziridinyl)methanone;
N-(4-Cyclohexylphenyl)-1-aziridincarboxamid; N-(4-cyclohexylphenyl)-1-aziridinecarboxamide;
2-[2-(1-Aziridinyl)ethoxy]-4-pyridinpyridincarbonsäure; 2-[2-(1-Aziridinyl)ethoxy]-4-pyridinepyridinecarboxylic acid;
6-[2-(1-Aziridinyl)ethoxy]-3-pyridinmethanamine; 6-[2-(1-aziridinyl)ethoxy]-3-pyridinemethanamine;
6-[2-(1-Aziridinyl)ethoxy]-2-pyridinpyridincarbonsäure; 6-[2-(1-Aziridinyl)ethoxy]-2-pyridinepyridinecarboxylic acid;
2-[2-(1-Aziridinyl)ethoxy]pyridin; 2-[2-(1-aziridinyl)ethoxy]pyridine;
2-[2-(1-Aziridinyl)ethoxy]-4-pyridinmethanamine; 2-[2-(1-aziridinyl)ethoxy]-4-pyridinemethanamine;
2-methyl-aziridine; 2-methylaziridines;
2-[1-(1-Aziridinylmethyl)propoxy]-pyridin; 2-[1-(1-aziridinylmethyl)propoxy]pyridine;
B) difunktionellen Aziridinen B) difunctional aziridines
N,N'-Hexamethylen-1,6-bis(1-aziridincarboxamid); N,N'-hexamethylene-1,6-bis(1-aziridinecarboxamide);
N,N'-(Methylendi-p-phenylen)bis(aziridin-1-carboxamid); N,N'-(methylenedi-p-phenylene)bis(aziridine-1-carboxamide);
N,N'-(Methylenedi-4,1-phenylen)bis[2-methyl-1-aziridincarboxamid];N,N'-(methylenedi-4,1-phenylene)bis[2-methyl-1-aziridinecarboxamide];
1-Aziridincarboxamid, N,N'-(3,3'-dimethyl[1, 1'-biphenyl]-4,4'-diyl)bis-;1-aziridinecarboxamide, N,N'-(3,3'-dimethyl[1,1'-biphenyl]-4,4'-diyl)bis-;
1-Aziridincarboxamid, N,N'-[1, 1'-biphenyl]-4,4'-diylbis-; 1-aziridinecarboxamide, N,N'-[1,1'-biphenyl]-4,4'-diylbis-;
1-Aziridincarboxamid, N,N'-(methylenedi-4,1-phenylen)bis-; 1-aziridinecarboxamide, N,N'-(methylenedi-4,1-phenylene)bis-;
1-Aziridincarboxamid, N,N'-(4-methyl-1,3-phenylen)bis-; 1-aziridinecarboxamide, N,N'-(4-methyl-1,3-phenylene)bis-;
1-Aziridincarboxamid, N,N'-(1,4-phenylendi-2,1-ethanediyl)bis-; 1-aziridinecarboxamide, N,N'-(1,4-phenylenedi-2,1-ethanediyl)bis-;
1-Aziridincarboxamid, N,N'-1,4-phenylenbis-; 1-aziridinecarboxamide, N,N'-1,4-phenylenebis-;
N,N'-(hexane-1,6-diyl)bis(2-methylaziridine-1-carboxamide); N,N'-(hexane-1,6-diyl)bis(2-methylaziridine-1-carboxamide);
N,N'-1,2-Ethanediylbis[1-aziridincarboxamid]; N,N'-1,2-ethanediylbis[1-aziridinecarboxamide];
N,N'-1,3-Propandiylbis[1-aziridincarboxamid]; N,N'-1,3-propanediylbis[1-aziridinecarboxamide];
N,N'-1,4-Butandiylbis[1-aziridincarboxamid]; N,N'-1,4-butanediylbis[1-aziridinecarboxamide];
N,N'-1,5-Pentandiylbis[1-aziridincarboxamid]; N,N'-1,5-pentanediylbis[1-aziridinecarboxamide];
N,N'-1,6-Hexanediylbis[1-aziridincarboxamid]; N,N'-1,6-hexanediylbis[1-aziridinecarboxamide];
N,N'-1,7-Heptanediylbis[1-aziridincarboxamid]; N,N'-1,7-heptanediylbis[1-aziridinecarboxamide];
N,N'-1,8-Octanediylbis[1-aziridincarboxamid]; N,N'-1,8-octanediylbis[1-aziridinecarboxamide];
N,N'-1,9-Nonanediylbis[1-aziridincarboxamid]; N,N'-1,10-Decanediylbis[1-aziridincarboxamid]; N,N'-1,9-nonanediylbis[1-aziridinecarboxamide]; N,N'-1,10-decanediylbis[1-aziridinecarboxamide];
1 -Aziridincarboxamid, N,N'-(3-hydroxy-1,5-pentandiyl)bis-1 -aziridinecarboxamide, N,N'-(3-hydroxy-1,5-pentanediyl)bis-
1 -Aziridincarboxamid, N,N'-1,5-naphthalenediylbis-; 1 -aziridinecarboxamide, N,N'-1,5-naphthalenediylbis-;
1 -Aziridincarboxamid, N,N'-(3,'-dimethoxy[1,1'-biphenyl]-4-4'-diyl)bis-1 -aziridinecarboxamide, N,N'-(3,'-dimethoxy[1,1'-biphenyl]-4,4'-diyl)bis-
; pentan ; pentane
1 -Aziridincarboxamid, N,N'-(methyl-1,3-phenylen)bis-; 1 -aziridinecarboxamide, N,N'-(methyl-1,3-phenylene)bis-;
1 -Aziridincarboxamid, N,N'-[1, 1'-biphenyl]-4,4'-diylbis-; 1 -aziridinecarboxamide, N,N'-[1,1'-biphenyl]-4,4'-diylbis-;
Poly(oxy-1,4-butanediyl),α-[[[3-[(1-aziridinylcarbonyl)amino]-4-methyl- phenyl]amino]carbonyl]-ω -[[[[3-[(1-aziridinylcarbonyl)amino]-4- methylphenyl]amino]carbonyl]oxy]-; Poly(oxy-1,4-butanediyl),α-[[[3-[(1-aziridinylcarbonyl)amino]-4-methyl-phenyl]amino]carbonyl]-ω-[[[[3-[(1- aziridinylcarbonyl)amino]-4-methylphenyl]amino]carbonyl]oxy]-;
N,N"-(methylenedi-4,1-phenylen)bis[N'-1-aziridinyl-harnstoff; N,N"-(methylenedi-4,1-phenylene)bis[N'-1-aziridinyl urea;
C) Trifunktionellen Aziridinen C) Trifunctional aziridines
Pentaerythritol tris[3-(1-aziridinyl)propionat]; pentaerythritol tris[3-(1-aziridinyl)propionate];
Trimethylolpropan tris[3-(2-methylaziridin-1-yl)propionat]; trimethylolpropane tris[3-(2-methylaziridin-1-yl)propionate];
Trimethylolpropan Tris[3-(aziridin-1-yl)propionat]; trimethylolpropane tris[3-(aziridin-1-yl)propionate];
1 -Aziridinpropionsäure, 2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-1,3- propandiylester; 1-Aziridinepropionic acid, 2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propanediyl ester;
1 -Aziridinpropionsäure, a-methyl-, 1, 1'-[2-[[3-(1-aziridinyl)-2-methyl-1- oxopropoxy]methyl]-2-ethyl-1,3-propandiyl]ester; 1-Aziridinepropionic acid, α-methyl, 1,1'-[2-[[3-(1-aziridinyl)-2-methyl-1-oxopropoxy]methyl]-2-ethyl-1,3-propanediyl]ester;
1 -Aziridinpropionsäure, 2-[[(1-aziridinylacetyl)oxy]methyl]-2-ethyl-1,3- propandiylester; 1-aziridinepropionic acid, 2-[[(1-aziridinylacetyl)oxy]methyl]-2-ethyl-1,3-propanediyl ester;
1-Aziridinpropionsäure, 2-methyl-, 1, 1',1"-(2-ethyl-1,2,3-pro- pantriyl)ester; 1-aziridinepropionic acid, 2-methyl, 1,1',1"-(2-ethyl-1,2,3-propanetriyl) ester;
1 -Aziridincarboxamid, N,N',N"-(methylidynetri-4,1-phenylen)tris; 1 -aziridinecarboxamide, N,N',N''-(methylidynetri-4,1-phenylene)tris;
1 -Aziridincarboxamid, N,N'-[[[6-[(1-aziridinylcarbonyl)amino]hexyl]- imino]bis(carbonylimino-6,1-hexanediyl)]bis-; 1 -aziridinecarboxamide, N,N'-[[[6-[(1-aziridinylcarbonyl)amino]hexyl]imino]bis(carbonylimino-6,1-hexanediyl)]bis-;
1-Aziridinpropionsäure, 2-methyl-, 1, 1'-[2-ethyl-2-[[3-(2-methyl-1- aziridinyl)-1-oxopropoxy]methyl]-1,3-propandiyl]ester; 1-aziridinepropionic acid, 2-methyl, 1,1'-[2-ethyl-2-[[3-(2-methyl-1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propanediyl]ester;
1-Aziridinpropionsäure, 1, 1'-[2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-1-aziridinepropionic acid, 1,1'-[2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-
2-ethyl-1,3-propandiyl]ester; 2-ethyl-1,3-propanediyl]ester;
1-Aziridinpropionsäure, 1, 1'-[2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-1-aziridinepropionic acid, 1,1'-[2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-
2-(hydroxymethyl)-1,3-propandiyl]ester; 2-(hydroxymethyl)-1,3-propanediyl]ester;
Poly(oxy-1,2-ethanediyl), α,α',α"-1,2,3-propantriyltris[ω -[[[[3-[(1- aziridinylcarbonyl)amino]-4-methylphenyl]amino]carbonyl]oxy]-; Aziri- dine, 1, 1',1"-(s-phenenyltricarbonyl)tris[2-methyl-; Poly(oxy-1,2-ethanediyl), α,α',α"-1,2,3-propanetriyltris[ω-[[[[3-[(1- aziridinylcarbonyl)amino]-4-methylphenyl]amino]carbonyl]oxy]-; aziridines, 1,1',1"-(s-phenenyltricarbonyl)tris[2-methyl-;
D) Tetrafunktionellen Aziridinen D) Tetrafunctional aziridines
Pentaerythritol tetrakis(β-aziridino)propionat; pentaerythritol tetrakis(β-aziridino)propionate;
1 -Aziridinpropionsäure, 1, 1'-[2,2-bis[[3-(1-aziridinyl)-1-oxopropoxy]- methyl]-1,3-propandiyl]ester; 1-Aziridinepropionic acid, 1,1'-[2,2-bis[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propanediyl]ester;
1 -Aziridinpropionsäure, 2-methyl-, 1, 1'-[2,2-bis[[3-(2-methyl-1-aziridi- nyl)-1-oxopropoxy]methyl]-1,3-propandiyl]ester; 1-Aziridinepropionic acid, 2-methyl, 1,1'-[2,2-bis[[3-(2-methyl-1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propanediyl]ester ;
1 -Aziridinethanol, α,α'-[[2,2-bis[2-hydroxy-3-(2-methyl-1-aziridinyl)- propoxy]methyl]-1,3-propandiyl]bis(oxymethylene)]bis[2-methyl-; Ethanon, 2,2,,2",2",-[[2,2,-bipyridin]-6,6,-diylbis(methylenenitrilo)]- tetrakis[1-(2-methyl-1-aziridinyl)-; 1 -Aziridineethanol, α,α'-[[2,2-bis[2-hydroxy-3-(2-methyl-1-aziridinyl)propoxy]methyl]-1,3-propanediyl]bis(oxymethylene)]bis [2-methyl-; ethanone, 2,2 ,, 2",2" , -[[2,2 , -bipyridine]-6,6 , -diylbis(methylenenitrilo)]-tetrakis[1-(2-methyl-1-aziridinyl)-;
1,5-Pentandion, 2-[bis[2-(2-methyl-1-aziridinyl)-2-oxoethyl]amino]-1,5- bis(2-methyl-1-aziridinyl)-; 1,5-pentanedione, 2-[bis[2-(2-methyl-1-aziridinyl)-2-oxoethyl]amino]-1,5-bis(2-methyl-1-aziridinyl)-;
Ethanon, 2,2',2",2",-(l,2-ethanediyldinitrilo)tetrakis[1-(2-methyl-1- aziridinyl)-; ethanone, 2,2',2",2" , -(1,2-ethanediyldinitrilo)tetrakis[1-(2-methyl-1-aziridinyl)-;
Methanon, 1, 1',1",1'"-( 1,4,5, 8-naphthalenetetrayl)tetrakis[1-(2-me- thyl-1-aziridinyl)-; methanone, 1,1',1",1'"-(1,4,5,8-naphthalenetetrayl)tetrakis[1-(2-methyl-1-aziridinyl)-;
1 -Aziridinethanol, α,α'-[[2,2-bis[2-hydroxy-3-(2-methyl-1-aziridi- nyl)propoxy]methyl]-1,3-propandiyl]bis(oxymethylen)]bis[2-methyl-; 1-Aziridinethanol, α,α'-[[2,2-bis[2-hydroxy-3-(2-methyl-1-aziridinyl)propoxy]methyl]-1,3-propanediyl]bis(oxymethylene)] bis[2-methyl-;
E) Multifunktionellen Aziridinen E) Multifunctional aziridines
1 -Aziridinpropionsäure, 1, 1'-[2-[[3-[3-(1-aziridinyl)-1-oxopropoxy]-2,2- bis[[3-(1-aziridinyl)-1-oxopropoxy]methyl]propoxy]methyl]-2-[[3-(1- aziridinyl)-1-oxopropoxy]methyl]-1,3-propandiyl]ester; 1-Aziridinepropionic acid, 1,1'-[2-[[3-[3-(1-aziridinyl)-1-oxopropoxy]-2,2-bis[[3-(1-aziridinyl)-1-oxopropoxy]methyl ]propoxy]methyl]-2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propanediyl]ester;
1 -Aziridinpropionsäure, 2-methyl-, 1, 1'-[2-[[3-[3-(1-aziridinyl)-1-ox- opropoxy]-2-(hydroxymethyl)-2-[[3-(2-methyl-1-aziridinyl)-1-ox- opropoxy]methyl]propoxy]methyl]-2-[[3-(2-methyl-1-aziridinyl)-1-ox- opropoxy]methyl]-1,3-propandiyl]ester; 1-Aziridinepropionic acid, 2-methyl-, 1,1'-[2-[[3-[3-(1-aziridinyl)-1-oxopropoxy]-2-(hydroxymethyl)-2-[[3-( 2-methyl-1-aziridinyl)-1-ox-opropoxy]methyl]propoxy]methyl]-2-[[3-(2-methyl-1-aziridinyl)-1-ox-opropoxy]methyl]-1,3 -propanediyl]ester;
1-Aziridinpropionsäure, β,2-dimethyl-, benzylhexaylhexamethyl- enester; 1-aziridinepropionic acid, β,2-dimethyl, benzylhexaylhexamethylene ester;
1-Aziridinpropionsäure, 2-ethyl-β-methyl-, benzylhexaylhexakis(meth- ylen)ester; sowie Mischungen und Kombinationen aus den zuvor genannten Aziri- dinen. 1-aziridinepropionic acid, 2-ethyl-β-methyl, benzylhexaylhexakis(methylene) ester; and mixtures and combinations of the aforementioned aziridines.
Besonders geeignete Aziridine sind hierbei:
Figure imgf000008_0001
Particularly suitable aziridines are:
Figure imgf000008_0001
N,N'-(Methylendi-p-phenylen)bis(aziridin-1-carboxamid),
Figure imgf000008_0002
N,N'-(methylenedi-p-phenylene)bis(aziridine-1-carboxamide),
Figure imgf000008_0002
Penta erythritol tris[3-(1-aziridinyl)propionat]
Figure imgf000008_0003
Penta erythritol tris[3-(1-aziridinyl)propionate]
Figure imgf000008_0003
N,N'-(hexan-1,6-diyl)bis(2-methylaziridine-1-carboxamid)
Figure imgf000008_0004
N,N'-(hexane-1,6-diyl)bis(2-methylaziridine-1-carboxamide)
Figure imgf000008_0004
Trimethylolpropan tris[3-(2-methylaziridin-1-yl)propionat]
Figure imgf000008_0005
Trimethylolpropan tris[3-(aziridin-1-yl)propionat] Trimethylolpropane tris[3-(2-methylaziridin-1-yl)propionate]
Figure imgf000008_0005
Trimethylolpropane tris[3-(aziridin-1-yl)propionate]
Weitere bevorzugte Aziridine sind in WO 2020/020714 und in WO 2021/148570 beschrieben. Der Offenbarungsgehalt dieser Patentanmeldungen bezüglich der genannten Aziridine wird mit zum Offenbarungsgehalt der Vor- liegenden Erfindung gemacht. Further preferred aziridines are described in WO 2020/020714 and in WO 2021/148570. The disclosure content of these patent applications with regard to the aziridines mentioned is included in the disclosure content of the present invention.
Besonders bevorzugte Aziridine sind dabei die nachfolgenden Verbindungen:
Figure imgf000009_0001
Particularly preferred aziridines are the following compounds:
Figure imgf000009_0001
Die genannten Aziridine sind teilweise im Handel erhältlich, z.B. von der Firma Menadiona (Barcelona, Spanien) oder Polyaziridine LLC (Palm Beach, USA). Some of the aziridines mentioned are commercially available, e.g. from Menadiona (Barcelona, Spain) or Polyaziridine LLC (Palm Beach, USA).
Bevorzugterweise ist der mindestens eine Hydrotalcit ausgewählt aus der Gruppe bestehend aus Verbindungen der allgemeinen Formel (M2+)1-x . (M3+)x . (OH)2 . (An-)x/n . m H2O wobei The at least one hydrotalcite is preferably selected from the group consisting of compounds of the general formula (M 2+ ) 1-x . (M 3+ ) x . (OH) 2 . (A n- ) x/n . m H 2 O where
M2+ eines oder mehrere der Metalle aus der Gruppe Mg, Ca, Sr oder Zn,M 2+ one or more of the metals from the group Mg, Ca, Sr or Zn,
M3+ AI oder B, M 3+ AI or B,
A ein Anion mit der Valenz n, bevorzugt OH-, HCO3-, CH3COO-, C6H5COO-, CO3 2-, SO4 2-, HPO4 2-, n 1 oder 2 ist, A is an anion with the valence n, preferably OH-, HCO 3 -, CH 3 COO-, C 6 H 5 COO-, CO 3 2- , SO 4 2- , HPO 4 2- , n is 1 or 2,
0 < x < 0,5 ist, und m eine Zahl von 0 bis 20 ist. 0 < x < 0.5, and m is a number from 0 to 20.
Insbesondere sind die Hydrotalcite ausgewählt aus der Gruppe bestehend aus Ca4AI2(OH)12 CO3 • 5 H2O, AI2O3 • 6 MgO • CO2 • 12 H2O, Mg4,5 AI2(OH)13 • CO3 • 3,5 H2O, Mg6AI2(OH)16 • CO3 • 4 H2O, 4 MgO • AIO3 • CO2 • 9 H2O, 4 MgO • AI2O3 • CO2 • 6 H2O, ZnO • 3 MgO • AI2O3 • CO2 • 8-9 H2O und ZnO • 3 MgO • AI2O3 • CO2 • 5-6 H2O. In particular, the hydrotalcites are selected from the group consisting of Ca 4 Al 2 (OH) 12 CO 3 • 5 H 2 O, Al 2 O 3 • 6 MgO • CO 2 • 12 H 2 O, Mg 4.5 Al 2 (OH ) 13 • CO 3 • 3.5 H 2 O, Mg 6 AI 2 (OH) 16 • CO 3 • 4 H 2 O, 4 MgO • AIO3 • CO 2 • 9 H 2 O, 4 MgO • AI 2 O 3 • CO 2 • 6 H 2 O, ZnO • 3 MgO • Al 2 O 3 • CO 2 • 8-9 H 2 O and ZnO • 3 MgO • Al 2 O 3 • CO 2 • 5-6 H 2 O.
Weiterhin ist es von Vorteil, wenn der mindestens eine Dawsonit ausgewählt aus der Gruppe bestehend aus Verbindungen der allgemeinen Formel
Figure imgf000010_0001
wobei Furthermore, it is advantageous if the at least one dawsonite is selected from the group consisting of compounds of the general formula
Figure imgf000010_0001
whereby
M ein Element, ausgewählt aus der Gruppe bestehend aus H, Li, Na, K, Mg1/2, Ca1/2, Sr1/2, Zn1/2; M an element selected from the group consisting of H, Li, Na, K, Mg 1/2 , Ca 1/2 , Sr 1/2 , Zn 1/2 ;
Z ein Substituent, ausgewählt aus der Gruppe bestehend aus CO2, SO2, (Cl2O7)1/2, B4O6, S2O2 (Thiosulfat) und/oder C2O2 (Oxalat); m wenn M Mg1/2, Ca1/2, ist, eine Zahl zwischen 1 und 2, in allen anderen Fäl- len eine Zahl zwischen 1 und 3; n eine Zahl zwischen 1 und 4; o eine Zahl zwischen 2 und 4; und p eine Zahl zwischen 0 und 30. Z is a substituent selected from the group consisting of CO2, SO2, (Cl 2 O 7 ) 1/2 , B 4 O 6 , S 2 O 2 (thiosulfate) and/or C 2 O 2 (oxalate); m if M is Mg 1/2 , Ca 1/2 , a number between 1 and 2, in all other cases a number between 1 and 3; n is a number between 1 and 4; o a number between 2 and 4; and p is a number between 0 and 30.
Insbesondere ist der mindestens eine Dawsonit ausgewählt aus der Gruppe be- stehend aus Kaliumalumocarbonat
Figure imgf000010_0002
Natriumalumo- thiosulfat
Figure imgf000010_0003
Kaliumalumosulfit
Figure imgf000010_0004
Calciumalumooxalat {(CaO)·(Al2O3)·(C2O2)2·5 H2O}, Magnesiumalumotet- .aborat {(MgO)-(AI2O3)·(B4O6)2·5 H2O}, Natriumalumodihydroxycarbonat, Kali- umalumodihydroxycarbonat sowie natürlich vorkommende Alkalialumocarbo- nat-Mineralien, wie z.B. Indigirit, Tunisit, Alumohydrocalcit und Strontiodresse- rit. In particular, the at least one dawsonite is selected from the group consisting of potassium aluminocarbonate
Figure imgf000010_0002
sodium aluminothiosulphate
Figure imgf000010_0003
potassium alumosulfite
Figure imgf000010_0004
Calcium alumooxalate {(CaO) (Al 2 O 3 ) (C 2 O 2 ) 2 .5H 2 O}, magnesium alumotet- .aborate {(MgO)-(AI 2 O 3 ) · (B 4 O 6 ) 2 · 5 H 2 O}, sodium alumodihydroxycarbonate, potassium alumodihydroxycarbonate and naturally occurring alkali alumocarbonate minerals such as indigirite, tunisit, alumohydrocalcite and Strontiodresserit.
Bevorzugt ist der mindestens eine Zeolith ausgewählt aus der Gruppe beste- hend aus Verbindungen der allgemeinen Formel The at least one zeolite is preferably selected from the group consisting of compounds of the general formula
Mx/n[(AIO2]x(SiO2)y W H20 wobei n die Ladung des Kations M; M x/n [(AIO 2 ] x (SiO 2 ) y W H20 where n is the charge of the cation M;
M ein Element der ersten oder zweiten Hauptgruppe, insbesondere Li, Na, K, Mg, Ca, Sr oder Ba; y:x einen Wert von 0,8 bis 15, bevorzugt von 0,8 bis 1,2, und w eine Zahl von 0 bis 300, bevorzugt von 0,5 bis 5 ist. M an element of the first or second main group, in particular Li, Na, K, Mg, Ca, Sr or Ba; y:x has a value from 0.8 to 15, preferably from 0.8 to 1.2, and w is a number from 0 to 300, preferably from 0.5 to 5.
Insbesondere ist der mindestens eine Zeolith ausgewählt aus der Gruppe be- stehend aus Natriumalumosilikaten der Formeln Na12Al12Si12O48·· 27 H2O [Zeo- lith A], Na6AI6Si5O24 • 2 NaX • 7,5 H2O (X= OH, Halogen, CIO4 [Sodalith]); Na6Al6Si3oO72 · 24 H2O; Na8Al8Si40O95 · 24 H2O; Na16Al16Si24O8 0 16 H2O; Na16Al16Si32O96 · 16 H2O; Na56Al56Si136O384· 250 H2O [Zeolith Y], Na86Al86Si106O384 .264 H2O [Zeolith X; K9Al9Si136O384 . 250 H2O [Zeolith Y, Na86Al86Si106O384 die Na-Atome der zuvorgenannten Zeolithe teilweise bzw. vollständig durch Li- , K-, Mg-, Ca-, Sr- oder Zn-Atome ausgetauscht sind, wie insbesondere (Na,K)10Al10Si22O64 · 20 H2O, Ca4,5Na3[(AIO2)12(SiO2)12 • 30 H2O und K9Na3[(AIO2)12SiO2)12] • 27 H2O. In particular, the at least one zeolite is selected from the group consisting of sodium aluminosilicates of the formulas Na 12 Al 12 Si 12 O 48 .27 H 2 O [zeolite A], Na 6 Al 6 Si 5 O 24 • 2 NaX • 7.5 H 2 O (X= OH, halogen, CIO 4 [sodalite]); Na6 Al6 Si30 O72.24 H2 O ; Na 8 Al 8 Si 40 O 95 · 24 H 2 O; Na 16 Al 16 Si 24 O 8 O 16 H 2 O; Na 16 Al 16 Si 32 O 96 · 16 H 2 O; Na 56 Al 56 Si 136 O 384.250 H 2 O [zeolite Y], Na 86 Al 86 Si 106 O 384.264 H 2 O [zeolite X; K9Al9Si136O384 . _ _ 250 H 2 O [zeolite Y, Na 86 Al 86 Si 106 O 384 the Na atoms of the aforementioned zeolites are partially or completely replaced by Li, K, Mg, Ca, Sr or Zn atoms, such as in particular (Na,K) 10 Al 10 Si 22 O 64 · 20 H 2 O, Ca 4.5 Na 3 [(AlO 2 ) 12 (SiO 2 ) 12 · 30 H 2 O and K 9 Na 3 [(AIO 2 ) 12 SiO 2 ) 12 ] • 27 H 2 O
Insbesondere ist es von Vorteil, wenn die Hydrotalcite, Zeolithe, Dawsonite o- der Mischungen hiervon als wasserfreie Formulierung eingesetzt werden. In particular, it is advantageous if the hydrotalcites, zeolites, dawsonites or mixtures thereof are used as an anhydrous formulation.
Bei der Stabilisator-Zusammensetzung gemäß der vorliegenden Erfindung ist es weiterhin vorteilhaft, wenn das Gewichtsverhältnis der Gesamtheit der Aziridin zur Gesamtheit des mindestens einen Hydrotalcites, Dawsoniten und/oder Ze- oliths 20:1 bis 1:20, bevorzugt von 10:1 bis 1:10, besonders bevorzugt von 5:1 bis 1:5 beträgt. In the stabilizer composition according to the present invention, it is further advantageous if the weight ratio of the total of the aziridine to all of the at least one hydrotalcite, dawsonite and/or zeolite is from 20:1 to 1:20, preferably from 10:1 to 1:10, particularly preferably from 5:1 to 1:5.
Zudem betrifft die vorliegende Erfindung die Verwendung einer zuvor beschrie- benen erfindungsgemäßen Stabilisator-Zusammensetzung zur Stabilisierung von Kondensationspolymeren gegen hydrolytischen Abbau. In addition, the present invention relates to the use of a stabilizer composition according to the invention as described above for stabilizing condensation polymers against hydrolytic degradation.
In einem weiteren Aspekt betrifft die vorliegende Erfindung ein Verfahren zur Stabilisierung von Kondensationspolymeren gegen hydrolytischen Abbau, bei dem dem Kondensationspolymer eine erfindungsgemäße, im Voranstehenden beschriebene Stabilisator-Zusammensetzung zugemischt oder mit dieser ge- blendet wird. In a further aspect, the present invention relates to a process for stabilizing condensation polymers against hydrolytic degradation, in which a stabilizer composition according to the invention, described above, is admixed to or blended with the condensation polymer.
Sowohl die erfindungsgemäße Verwendung bzw. das erfindungsgemäße Ver- fahren zeichnen sich vorteilhafterweise dadurch aus, dass die Stabilisator-Zu- sammensetzung in einem Gewichtsverhältnis von 0,01 bis 10 Gew.-%, bevor- zugt von 0,05 bis 5 Gew.-%, besonders bevorzugt von 0,1 bis 3 % Gew.-% bezo- gen auf das Polykondensationspolymere verwendet bzw. zugemischt wird. Both the use according to the invention and the method according to the invention are advantageously characterized in that the stabilizer composition is present in a weight ratio of from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight. %, particularly preferably from 0.1 to 3% by weight, based on the polycondensation polymer, is used or mixed in.
Zudem betrifft die vorliegende Erfindung eine hydrolysestabilisierte Zusam- mensetzung, enthaltend oder bestehend aus mindestens einem Kondensati- onspolymer sowie einer erfindungsgemäßen Stabilisator-Zusammensetzung nach einem der Ansprüche 1 bis 8. In addition, the present invention relates to a hydrolysis-stabilized composition containing or consisting of at least one condensation polymer and a stabilizer composition according to the invention according to any one of claims 1 to 8.
In einer bevorzugten Ausführungsform der Verwendung, des Verfahrens oder der Zusammensetzung ist vorgesehen, dass das Kondensationspolymere aus- gewählt ist aus der Gruppe bestehend aus a) Polyamiden, wie z.B. Polyamid-6, 6.6, 6.9, 6.10, 4.6, 4.10, 6.12, 10.10, 10.12, 12.12, Polyamid 4, Polyamid, 7, Polyamid 8, Polyamid 9, Polyamid 11, Polyamid 12 sowie (teil-)aromatische Polyamide wie z.B. Polyphtha- lamide, z.B. hergestellt aus Terephthalsäure und/oder Isophthalsäure und aliphatischen Diaminen wie z.B. Hexamethylendiamin oder m-Xyly- lendiamin oder aus aliphatischen Dicarbonsäuren wie z.B. Adipinsäure o- der Sebazinsäure und aromatischen Diaminen wie z.B. 1,4- oder 1,3-Dia- minobenzol, bezeichnet z.B. als Polyamid 6T, Polyamid 9T, Polyamid 61, Polyamid-6-3-T, Blends von unterschiedlichen Polyamiden wie z.B. PA-6 und PA 6.6, PA6T und PA6I, PA-6.6 und PA6T bzw. Blends von Polyamiden und Polyolefinen wie z.B. PA/PP oder PA/PE. b) Polyestern aus aliphatischen oder aromatischen Dicarbonsäuren und Di- olen oder aus Hydroxy-Carbonsäuren, insbesondere aliphatischen Poly- estern, wie z.B. Polyethylenterephthalat (PET), Polybutylenterephthalat (PBT), Polytrimethylenterephthalat (PTT), Polypropylenterephthalat (PPT), Polyethylennaphthylat (PEN), Poly-1,4-dimethylol-cyclo-hexan- terephthalat, Polyhydroxybenzoat, Polyhydroxynaphthalat, Polymilch- säure (PLA), Polyhydroxybutyrat (PHB), Polyhydroxyvalerat (PHV), Polyb- utylensuccinat (PBS), Polybutylensuccinatadipat (PBSA), Polyethylensuc- cinat, Polycaprolacton, c) Polycarbonaten, Polyestercarbonaten, sowie Blends wie z.B. PC/ABS, PC/PBT, PC/PET/PBT, PC/PA, d) sowie Mischungen, Kombinationen oder Blends aus zwei oder mehr der zuvor genannten Polymeren. A preferred embodiment of the use, the method or the composition provides that the condensation polymer is selected from the group consisting of a) polyamides, such as polyamide-6, 6.6, 6.9, 6.10, 4.6, 4.10, 6.12, 10.10 , 10.12, 12.12, polyamide 4, polyamide 7, polyamide 8, polyamide 9, polyamide 11, polyamide 12 and (partly) aromatic polyamides such as polyphthalamides, for example produced from terephthalic acid and/or isophthalic acid and aliphatic diamines such as hexamethylenediamine or m-xylylenediamine or from aliphatic dicarboxylic acids such as adipic acid o- of sebacic acid and aromatic diamines such as 1,4- or 1,3-diaminobenzene, referred to, for example, as polyamide 6T, polyamide 9T, polyamide 61, polyamide 6-3-T, blends of different polyamides such as PA-6 and PA 6.6, PA6T and PA6I, PA-6.6 and PA6T or blends of polyamides and polyolefins such as PA/PP or PA/PE. b) polyesters made from aliphatic or aromatic dicarboxylic acids and diols or from hydroxycarboxylic acids, in particular aliphatic polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polypropylene terephthalate (PPT), polyethylene naphthylate (PEN) , poly-1,4-dimethylol-cyclohexane terephthalate, polyhydroxybenzoate, polyhydroxynaphthalate, polylactic acid (PLA), polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polyethylene succinate cinate, polycaprolactone, c) polycarbonates, polyester carbonates, and blends such as PC/ABS, PC/PBT, PC/PET/PBT, PC/PA, d) and mixtures, combinations or blends of two or more of the aforementioned polymers.
Weiterhin können die unter a) bis c) angegebenen Polymeren sowohl amorphe als auch (teil-) kristalline Morphologien aufweisen. Furthermore, the polymers specified under a) to c) can have both amorphous and (partially) crystalline morphologies.
Besonders bevorzugte Polyester sind hierbei aliphatische Polyester, d. h. Poly- ester, die aus aliphatischen Dicarbonsäuren und aliphatischen Diolen bzw. aus aliphatischen Lactonen hergestellt werden können. Particularly preferred polyesters here are aliphatic polyesters, i. H. Polyester which can be produced from aliphatic dicarboxylic acids and aliphatic diols or from aliphatic lactones.
Geeignete Diole für aliphatische Polyester sind beispielsweise Ethylenglycol, 1,3-Propandiol, 1,2-Propandiol,1,4-Butandiol, Neopentylglykol, 1,5-Pentandi- ol, 1,6-Hexandiol, 2,5-Hexandiol, 3-Methyl-2,4pentandiol, 2-Methyl-2,4-pen- tandiol, 2,2,4-Trimethyl-1,3-pentandiol, 1,8-Octandiol, 1,10-Decandiol, 1,12- Dodecandiol, -1,6,2-Ethylhexandiol-1,3, 2,2-Diethylpropandiol-1,3, 2,2-Bis-(4- hydroxycyclohexyl)-propan, 2,2-Bis-(4-hydroxypropoxyphenyl)-propan, 1,4- Cyclohexandiol, 1,3-Cyclohexandiol, 1,4-Cyclohexandimethanol, 1,3-Cyclohe- xandimethanol. Examples of suitable diols for aliphatic polyesters are ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, 3 -Methyl-2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol , -1,6,2-ethylhexanediol-1,3, 2,2-diethylpropanediol-1,3, 2,2-bis(4-hydroxycyclohexyl)propane, 2,2-bis(4-hydroxypropoxyphenyl)- propane, 1,4- Cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol.
Geeignete Dicarbonsaäuren sind beispielsweise Malonsäure, Dimethylmalon- säure, Bernsteinsäure, Glutarsäure, Adipinsäure, Pimelinsäure, Suberinsäure, Azelainsäure, Sebacinsäure, Dodecandisäure, Brassylsäure, Tetradecan- disäure, Hexadecandisäure, Cyclohexan-1,3-dicarbonsäure oder Cyclohexan- 1,4-dicarbonsäure. Examples of suitable dicarboxylic acids are malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, hexadecanedioic acid, cyclohexane-1,3-dicarboxylic acid or cyclohexane-1,4-dicarboxylic acid.
Neben aliphatischen Strukturen können in untergeordnetem Maße bis 20 mol % auch aromatische Strukturen vorliegen, bevorzugt kleiner 10 mol%, ganz besonders bevorzugt kleiner 1 mol%. Geeignete aromatische Strukturen sind bei Diolen Hydrochinon, Resorcin, 2,6-Naphthalindiol, 1,8-Naphthalindiol, Bi- sphenol-A, bei Dicarbonsäuren Terephthalsäure, Isophthalsäure, Naphthalin- 2,6-dicarbonsäure, Beispiel für eine heterocyclische aromatische Dicarbon- säure ist 2,5-Furandicarbonsäure. In addition to aliphatic structures, aromatic structures can also be present to a minor extent, up to 20 mol %, preferably less than 10 mol %, very particularly preferably less than 1 mol %. Suitable aromatic structures are hydroquinone, resorcinol, 2,6-naphthalenediol, 1,8-naphthalenediol, bisphenol-A in the case of diols, and terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid in the case of dicarboxylic acids, an example of a heterocyclic aromatic dicarboxylic acid is 2,5-furandicarboxylic acid.
Geeignete Hydroxycarbonsäuren sind beispielsweise Milchsäure, Glycolsäure, 4-Hydroxybuttersäure, 3-Hydroxybuttersäure oder 3-Hydroxyvaleriansäure, eine Hydroxycarbonsäure mit aromatischen Anteilen ist Mandelsäure. Suitable hydroxycarboxylic acids are, for example, lactic acid, glycolic acid, 4-hydroxybutyric acid, 3-hydroxybutyric acid or 3-hydroxyvaleric acid, and a hydroxycarboxylic acid with aromatic components is mandelic acid.
Weitere bevorzugte Polyester sind insbesondere Polybutylenterephthalat (PBT) und Copolymere von 1,4-Butandiol mit Terephthalsäure, Adipinsäure o- der Sebazinsäure. Other preferred polyesters are, in particular, polybutylene terephthalate (PBT) and copolymers of 1,4-butanediol with terephthalic acid, adipic acid or sebacic acid.
Bevorzugte Polyamide sind insbesondere Polyamid-6, Polyamid-6.6, Blends von Polyamid 6 mit Polyamid 6.6, Polyamid-10.10, Polyamid-10.12, Polyamid-12.12, Polyamid-11 und Polyamid-12. Preferred polyamides are in particular polyamide 6, polyamide 6.6, blends of polyamide 6 with polyamide 6.6, polyamide 10.10, polyamide 10.12, polyamide 12.12, polyamide 11 and polyamide 12.
Zusätzlich können die Zusammensetzungen weitere Zusatzstoffe enthalten, ausgewählt aus der Gruppe bestehend aus sekundären Antioxidantien, UV-Ab- sorber, der Lichtstabilisatoren, der Metalldesaktivatoren, der Füllstoffdesakti- vatoren, der Antiozonantien, Nukleierungsmittel, Antinukleierungsmittel, Schlagzähigkeitsverbesserer, Weichmacher, Gleitmittel, Rheologiemodifikato- ren, Thixotropiemittel, Kettenverlängerer, Verarbeitungshilfsmittel, Entfor- mungshilfsmittel, Flammschutzmittel, Pigmente, Farbstoffe, optische Aufhel- ler, antimikrobielle Wirkstoffe, Antistatika, Slipmittel, Antiblockmittel, Kopp- lungsmittel, Vernetzungsmittel, Antivernetzungsmittel, Hydrophilisierungsmit- tel, Hydrophobierungsmittel, Hydrolysestabilisatoren, Haftvermittler, Disper- giermittel, Kompatibilisatoren, Sauerstofffänger, Säurefänger, Treibmittel, Ab- bau-Additive, Entschäumungshilfsmittel, Geruchsfänger, Markierungsmittel, Antifoggingmittel, Füllstoffe und Verstärkungsstoffe eingesetzt werden. In addition, the compositions can contain other additives selected from the group consisting of secondary antioxidants, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact modifiers, plasticizers, lubricants, rheology modifiers , thixotropic agents, chain extenders, processing aids, additives, flame retardants, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anticrosslinking agents, hydrophilizing agents, hydrophobing agents, hydrolysis stabilizers, adhesion promoters, dispersing agents, compatibilizers, oxygen scavengers, acid scavengers, Blowing agents, degradation additives, defoaming aids, odor traps, marking agents, antifogging agents, fillers and reinforcing materials are used.
In bevorzugter Ausführungsform enthalten die Zusammensetzungen insbeson- dere Phosphite oder Phosphonite, Füllstoffe oder Säurefänger. In a preferred embodiment, the compositions contain, in particular, phosphites or phosphonites, fillers or acid scavengers.
Geeignete phenolische Antioxidantien sind beispielsweise: Examples of suitable phenolic antioxidants are:
Alkylierte Monophenole, wie z.B. 2,6-Di-tert-butyl-4-methylphenol, 2-tert- Butyl-4,6-dimethylphenol, 2,6-Di-tert-butyl-4-ethylphenol, 2,6-Di-tert-butyl-4- n-butylphenol, 2,6-Di-tert-butyl-4-isobutylphenol, 2,6-Dicyclopentyl-4-methyl- phenol, 2-(α-Methylcyclohexyl)-4,6-dimethylphenol, 2,6-Dioctadecyl-4-me- thylphenol, 2,4,6-Tricyclohexylphenol, 2,6-Di-tert-butyl-4-methoxymethyl- phenol, lineare oder verzweigte Nonylphenole, wie z.B. 2,6-Dinonyl-4-methyl- phenol, 2,4-Dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-Dimethyl-6-(l'-me- thylheptadec-1'-yl)phenol, 2,4-Dimethyl-6-(l'-methyltridec-1'-yl)phenol und Mischungen hiervon; Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di -tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methyl-phenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol , 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethyl- phenol, linear or branched nonylphenols such as 2,6-dinonyl- 4-methyl-phenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures thereof;
Alkylthiomethylphenole, wie z.B. 2,4-Dioctylthiomethyl-6-tert-butylphenol, 2,4-Dioctylthiomethyl-6-methylphenol, 2,4-Dioctylthiomethyl-6-ethylphenol, 2,6-Didodecylthiomethyl-4-nonylphenol; alkylthiomethyl phenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol;
Hydrochinone und alkylierte Hydrochinone, wie z.B. 2,6-Di-tert-butyl-4-me- thyoxyphenol, 2,5-Di-tert-butylhydrochinon, 2,5-Di-tert-amylhydrochinon, 2,6- Diphenyl-4-octadecyloxyphenol, 2,6-Di-tert-butylhydrochinon, 2,5-Di-tert- butyl-4-hydroxyanisol, 3,5-Di-tert-butyl-4-hydroxyanisol, 3,5-Di-tert-butyl-4- hydroxyphenylstearat, Bis(3,5-di-tert-butyl-4-hydroxylphenyl)adipat; Hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methyloxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4 -octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl -4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxylphenyl)adipate;
Tocopherole, wie z.B. α-, β-, γ-, δ-Tocopherol und Mischungen aus diesen (Vi- tamin E); Hydroxylierte Thiodiphenylether, wie z.B. 2,2'-Thiobis(6-tert-butyl-4-methyl- phenol), 2,2'-Thiobis(4-octylphenol), 4,4'-Thiobis(6-tert-butyl-3-methyl- phenol), 4,4'-Thiobis(6-tert-butyl-2-methylphenol), 4,4'-Thiobis(3,6-di-sec- amylphenol), 4,4'-Bis(2,6-dimethyl-4-hydroxyphenyl)disulfid; Tocopherols, such as α-, β-, γ-, δ-tocopherol and mixtures of these (vitamin E); Hydroxylated thiodiphenyl ethers such as 2,2'-thiobis(6-tert-butyl-4-methyl-phenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl- 3-methyl- phenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-di-secamylphenol), 4,4'-bis( 2,6-dimethyl-4-hydroxyphenyl) disulfide;
Alkylidenbisphenole, wie z.B. 2,2'Methylenbis(6-tert-butyl-4-methylphenol), 2,2'-Methylenbis(6-tert-butyl-4-ethylphenol), 2,2'-Methylenbis[4-methyl-6-(α- methylcyclohexyl)phenol], 2,2'-Methylenbis(4-methyl-6-cyclhexylphenol), 2,2'- Methylenbis(6-nonyl-4-methylphenol), 2,2'-Methylenbis(4,6-di-tert-butylphe- nol), 2,2'-Ethylidenbis(4,6-di-tert-butylphenol), 2,2'-Ethylidenbis(6-tert-butyl- 4-isobutylphenol), 2,2'-Methylenbis[6-(a-methylbenzyl)-4-nonylphenol], 2,2'- Methylenbis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-Methylenbis(2,6-di- tert-butylphenol, 4,4'-Methylenbis(6-tert-butyl-2-methylphenol), 1,1-bis(5- tert-butyl-4-hydroxy-2-methylphenyl)butan, 2,6-Bis(3-tert-butyl-5-methyl-2- hydroxybenzyl)-4-methylphenol, 1,1,3-Tris(5-tert-butyl-4-hydroxy-2-methyl- phenyl)butan, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecyl- mercaptobutan, Ethylenglycol-bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)buty- rat], Bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclo-pentadien, Bis[2-(3'- tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]tereph- thalat, 1,1-Bis-(3,5-dimethyl-2-hydroxyphenyl)butan, 2,2-Bis(3,5-di-tert-butyl- 4-hydroxyphenyl)propan, 2,2-Bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n- dodecylmercaptobutan, 1,1,5,5-Tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)- pentan; Alkylidenebisphenols such as 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl- 6-(α-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4 ,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2, 2'-methylenebis[6-(a-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6 -di-tert-butylphenol, 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6 -bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methyl-phenyl)butane, 1, 1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)buty - rat], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3'- tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2, 2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1, 1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane;
O-, N- und S-Benzyl-Verbindungen, wie z.B. 3,5,3',5'-Tetra-tert-butyl-4,4'- dihydroxydibenzylether, Octadecyl-4-hydroxy-3,5-dimethylbenzylmercapto- acetat, Tridecyl-4-hydroxy-3,5-di-tert-butyl-benzyl-mercaptoacetat, Tris(3,5-di- tert-butyl-4-hydroxybenzyl)amin, Bis(4-tert-butyl-3-hydroxy-2,6-dimethyl- benzyl)dithioterephthalat, Bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfid, Iso- octyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetat; O-, N- and S-benzyl compounds such as 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate , tridecyl 4-hydroxy-3,5-di-tert-butyl-benzyl-mercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy -2,6-dimethyl-benzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate;
Hydroxybenzylierte Malonate, wie z.B. Dioctadecyl-2, 2-bis(3,5-di-tert-butyl-2- hydroxybenzyl)malonat, Dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methyl- benzyl)malonat, Didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxy- benzyl)malonat, Bis[4-( 1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert- butyl-4-hydroxybenzyl)malonat; Aromatische Hydroxybenzylverbindungen, wie z.B. 1,3,5-Tris(3,5-di-tert-butyl- 4-hydroxybenzyl)-2,4,6-trimethylbenzol, 1,4-Bis(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,3,5,6-tetramethylbenzol, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxy- benzyl)phenol; Hydroxybenzylated malonates such as dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methyl-benzyl) malonate, didodecylmercaptoethyl 2,2-bis(3,5-di-tert-butyl-4-hydroxy-benzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2- bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate; Aromatic hydroxybenzyl compounds such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert- butyl-4-hydroxy-benzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)phenol;
Triazinverbindungen, wie z.B. 2,4-Bis(octylmercapto)-6-(3,5-di-tert-butyl-4- hydroxyanilino)-1,3,5-triazin, 2-Octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hyd- roxyanilino)-1,3,5-triazin, 2-Octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxy- phenoxy)-1,3,5-triazin, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3- triazin, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurat, 1,3,5-Tris(4- tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurat, 2,4,6-Tris(3,5-di-tert- butyl-4-hydroxphenylethyl)-1,3,5-triazin, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroy- phenylpropionyl)hexahydro-1,3,5-triazin, 1,3,5-Tris(3,5-dicyclohexyl-4-hydro- xybenzyl)isocyanurat; Triazine compounds such as 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3 ,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxy-phenoxy) -1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3, 5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3, 5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro-1,3 ,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate;
Benzylphosphonate, wie z.B. Dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphos- phonat, Dietyhl-3,5-di-tert-butyl-4-hydroxybenzylphosphonat, Dioctadecyl-Benzyl phosphonates such as dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl
3.5-di-tert-butyl-4-hydroxybenzylphosphonat, Dioctadecyl-5-tert-butyl-4-hyd- roxy-3-methylbenzylphosphonat, das Calciumsalz des Monoethylesters der3.5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of
3.5-Di-tert-butyl-4-hydroxybenzylphosphonsäure; 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid;
Acylaminophenole, wie z.B.4-Hydroxylauranilid, 4-Hydroxystearanilid, Octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl)carbamat; acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate;
Ester der β-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionsäure mit ein- oder mehrwertigen Alkoholen, z.B. Methanol, Ethanol, n-Octanol, i-Octanol, Octade- canol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopen- tylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythri- tol, Tris(hydroxyethyl)isocyanurat, N,N'-Bis(hydroxyethyl)oxamid, 3-Thiaunde- canol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydro- xymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octan; Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, e.g. methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol , 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;
Ester der β-(5-tert-Butyl-4-hydroxy-3-methylphenyl)propionsäure mit ein- oder mehrwertigen Alkoholen, z.B. Methanol, Ethanol, n-Octanol, i-Octanol, Octade- canol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopen- tylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythri- tol, Tris(hydroxyethyl)isocyanurat, N,N'-bis(hydroxyethyl)oxamid, 3-Thiaunde- canol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydro- xymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octan, 3,9-Bis[2-{3-(3-tert-butyl- 4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetrao- xaspiro[5.5]undecan; Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols, for example methanol, ethanol, n-octanol, i-octanol, octade- canol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl )oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, 3,9-bis[2-{ 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane;
Ester der β-(3,5-Dicyclohexyl-4-hydroxyphenyl)propionsäure mit ein- oder mehrwertigen Alkoholen, z.B. Methanol, Ethanol, Octanol, Octadecanol, 1,6- Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythritol, Tris- (hydroxyethyl)isocyanurat, N,N'-bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3- Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2- Propanediol, Neopentyl Glycol, Thiodiethylene Glycol, Diethylene Glycol, Triethylene Glycol, Pentaerythritol, Tris-(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-
1-phospha-2,6,7-trioxabicyclo[2.2.2]octan; 1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;
Ester der (3,5-Di-tert-butyl-4-hydroxyphenyl)essigsäure mit ein- oder mehrwer- tigen Alkoholen, z.B. Methanol, Ethanol, Octanol, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylen- glycol, Diethylenglycol, Triethylenglycol, Penta erythritol, Tris(hydroxyethyl)iso- cyanurat, N,N'-bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3-Thiapentadeca- nol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-1-phospha- 2,6,7-trioxabicyclo[2.2.2]octan; Esters of (3,5-di-tert-butyl-4-hydroxyphenyl)acetic acid with monohydric or polyhydric alcohols, e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;
Amide der β-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionsäure, wie z.B. N,N'- Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylendiamid, N,N'- Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylendiamid, N,N'- Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylendiamid, N,N'-Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, such as N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N' - Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'- Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-
Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazid, N,N'-Bis[2-(3-[3,5-di- tert-butyl-4-hydroxy-phenyl]propionyloxy)ethyl]oxamid (Naugard®XL-1, ver- trieben durch Uniroyal); Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl ]oxamide (Naugard® XL-1 sold by Uniroyal);
Ascorbinsäure (Vitamin C). Ascorbic acid (vitamin C).
Besonders bevorzugte phenolische Antioxidantien sind die folgenden Struktu- ren:
Figure imgf000019_0001
Figure imgf000020_0001
Particularly preferred phenolic antioxidants are the following structures:
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
wobei in den zuvor genannten Verbindungen n eine ganze Zahl ist und bei zwi- schen 2 und 10 liegt.
Figure imgf000021_0001
where in the aforementioned compounds n is an integer and is between 2 and 10.
Weitere bevorzugte phenolische Antioxidantien sind auf nachwachsenden Roh- stoffen basierende phenolische Antioxidantien wie z. B. a-, β-, γ-, δ-Tocopherol und Mischungen aus diesen (Vitamin E), Tocotrienole, Tocomonoenole, Ubichi- nol, Hydroxytyrosol, Flavonoide and Flavonole wie z.B. Chrysin, Quercitin, Hes- peridin, Neohesperidin, Naringin, Morin, Kaempferol, Fisetin, Datiscetin, Lute- olin, Apigenin, Taxifolin, Isoflavone wie z.B. Genistein, Genistin, Daidzein, Daidzin, Formononetin, Anthocyane, wie z.B. Delphinidin und Malvidin, Cur- cumin, Carnosolsäure, Carnosol, Rosmarinsäure, Tannin und Resveratrol sowie Carotenoide mit alkoholischen Gruppen ,wie z.B. beta-Cryptoxanthin, Lutein, Zeaxanthin oder Astaxanthin. Other preferred phenolic antioxidants are based on renewable raw materials phenolic antioxidants such. B. a-, β-, γ-, δ-tocopherol and mixtures of these (vitamin E), tocotrienols, tocomonoenols, ubiquinol, hydroxytyrosol, flavonoids and flavonols such as e.g. chrysin, quercitin, hesperidin, neohesperidin, naringin, Morin, kaempferol, fisetin, datiscetin, luteolin, apigenin, taxifolin, isoflavones such as genistein, genistin, daidzein, daidzin, formononetin, anthocyanins such as delphinidin and malvidin, curcumin, carnosic acid, carnosol, rosmarinic acid, tannin and resveratrol and carotenoids with alcoholic groups, such as beta-cryptoxanthin, lutein, zeaxanthin or astaxanthin.
Geeignete aminische Antioxidantien sind beispielsweise: Examples of suitable aminic antioxidants are:
N,N'-Di-isopropyl-p-phenylendiamin, N,N'-Di-sec-butyl-p-phenylendiamin, N,N'-Bis(1,4-dimethylpentyl)-p-phenylendiamin, N,N'-Bis(1-ethyl-3-methyl- pentyl)-p-phenylendiamin, N,N'-Bis(1-methylheptyl)-p-phenylendiamin, N,N'- Dicyclohexyl-p-phenylendiamin, N,N'-Diphenyl-p-phenylendiamin, N,N'- Bis(2-naphthyl)-p-phenylendiamin, N-lsopropyl-N'-phenyl-p-phenylendiamin, N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylen-diamin, N-(1-Methylheptyl)-N'- phenyl-p-phenylendiamin, N-Cyclohexyl-N'-phenyl-p-phenylendiamin, 4-(p- Toluolsulfamoyl)diphenylamin, N,N'-Dimethyl-N,N'-di-sec-butyl-p-phenylen- diamin, Diphenylamin, N-Allyldiphenylamin, 4-lsopropoxydiphenylamin, N- Phenyl-1-naphthylamin, N-(4-tert-Octylphenyl)-1-naphthylamin, N-Phenyl-2- naphthylamin, octyliertes Diphenylamin, z.B. p,p'-Di-tert-octyldiphenylamin, 4-n-Butylaminophenol, 4-Butyrylaminophenol, 4-Nonanoylaminophenol, 4- Dodecanoylaminophenol, 4-Octadecanoylamino-phenol, Bis(4-methoxyphe- nyl)amin, 2,6-Di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-Diami- nodiphenylmethan, 4,4'-Diaminodiphenylmethan, N,N,N',N'-Tetra-methyl- 4,4'-diaminodiphenylmethan, 1,2-Bis[(2-methyl-phenyl)amino]ethan, 1,2- Bis(phenylamino)propan, (o-Tolyl)biguanid, Bis[4-(1',3'-dimethylbutyl)phe- nyl]amin, tert-octyliertes N-Phenyl-1-naphthylamin, ein Gemisch aus mono- und dialkylierten tert-Butyl/tert-Octyldiphenylaminen, ein Gemisch aus mono- und dialkylierten Nonyldiphenylaminen, ein Gemisch aus mono- und dialkylierten Dodecyldiphenylaminen, ein Gemisch aus mono- und dialkylier- ten Isopropyl/lsohexyl-diphenylaminen, ein Gemisch aus mono- und dialky- lierten tert-Butyldiphenylaminen, 2,3-Dihydro-3,3-dimethyl-4H-1,4-benzothi- azin, Phenothiazin, ein Gemisch aus mono- und dialkylierten tert-Butyl/tert- Octylphenothiazinen, ein Gemisch aus mono- und dialkylierten tert-Octylphe- nothiazinen, N-Allylphenothiazin, N,N,N',N'-Tetraphenyl-1,4-diaminobut-2- en sowie Mischungen oder Kombinationen hiervon. N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N' -Bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-Bis(1-methylheptyl)-p-phenylenediamine, N,N'-Dicyclohexyl-p-phenylenediamine, N,N'- Diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl- p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p- toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4 -tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine eg p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol , 4-octadecanoylamino-phenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N ,N,N',N'-Tetra-methyl- 4,4'-diaminodiphenylmethane, 1,2-bis[(2-methyl-phenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o- tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and di-alkylated tert-butyl/tert-octyldiphenylamines mixture of mono- and di-alkylated nonyldiphenylamines, a mixture of mono- and di-alkylated dodecyldiphenylamines, a mixture of mono- and d ialkylated isopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono - and dialkylated tert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene as well as Mixtures or combinations thereof.
Bevorzugte aminische Antioxidantien sind: N,N'-Di-isopropyl-p-phenylendia- min, N,N'-Di-sec-butyl-p-phenylendiamin, N,N'-Bis(1,4-dimethylpentyl)-p-phe- nylendiamin, N,N'-Bis(1-ethyl-3-methylpentyl)-p-phenylendiamin, N,N'-Bis(1- methylheptyl)-p-phenylendiamin, N,N'-Dicyclohexyl-p-phenylendiamin, N,N'- Diphenyl-p-phenylendiamin, N,N'-Bis(2-naphthyl)-p-phenylendiamin, N-Isop- ropyl-N'-phenyl-p-phenylendiamin, N-(1,3-Dimethylbutyl)-N'-phenyl-p-pheny- len-diamin, N-(1-Methylheptyl)-N'-phenyl-p-phenylendiamin, N-Cyclohexyl-N'- phenyl-p-phenylendiamin Preferred amine antioxidants are: N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p -phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p- phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3 -dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine
Besonders bevorzugte aminische Antioxidantien sind die Strukturen:
Figure imgf000022_0001
Particularly preferred aminic antioxidants are the structures:
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000023_0001
Bevorzugte Hydroxylamine bzw. N-oxide (Nitrone) sind z.B. N,N-Dialkylhydro- xylamine, N,N-Dibenzylhydroxylamin, N,N-Dilaurylhydroxylamin, N,N-Distea- rylhydroxylamin, N-Benzyl-α-phenylnitron, N-Octadecyl-a-hexadecylnitron, sowie Genox EP (SI Group) gemäß der Formel:
Figure imgf000023_0002
Preferred hydroxylamines or N-oxides (nitrones) are, for example, N,N-dialkylhydroxylamine, N,N-dibenzylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-distearylhydroxylamine, N-benzyl-α-phenylnitrone, N- Octadecyl-a-hexadecylnitrone, as well as Genox EP (SI Group) according to the formula:
Figure imgf000023_0002
Geeignete Lactone sind Benzofuranone und Indolinone wie z.B. 3-(4-(2-ace- toxyethoxy)-phenyl]-5,7-di-tert-butyl-benzofuran-2-on, 5,7-di-tert-butyl-3- [4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-on, 3,3'-bis[5,7-di-tert-butyl- 3-(4-(2-hydroxyethoxy]phenyl )benzofuran-2-on), 5,7-di-tert-butyl-3-(4- ethoxyphenyl)benzofuran-2-on, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di- tert-butyl-benzofuran-2-on, 3-(3,5-dimethyl-4-pivaloyloxyphenyl )-5,7-di- tert-butyl-benzofuran-2-on, 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-ben- zofuran-2-on, 3-(2,3-di- methylphenyl)-5,7-di-tert-butyl-benzofuran-2-on, sowie Lactone, die zusätzlich Phosphitgruppen beinhalten wie z.B.
Figure imgf000023_0003
Suitable lactones are benzofuranones and indolinones such as 3-(4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl- 3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-(2-hydroxyethoxy)phenyl)benzofuran-2 -one), 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl -benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7 -di-tert-butyl-benzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, and lactones which additionally contain phosphite groups such as
Figure imgf000023_0003
Figure imgf000024_0001
Figure imgf000024_0001
Bevorzugte Füllstoffe sind Calciumcarbonat, Silikate, Talkum, Glimmer, Kaolin, Metalloxide und Metallhydroxide, Ruß, Graphit, Holzmehl oder Fasern von Na- turprodukten wie z.B. Cellulose. Weitere geeignete Füllstoffe sind Hydrotalcite oder Zeolithe oder Schichtsilikate wie z.B. Montmorillonit, Bentonit, Beidelit, Mica, Hectorit, Saponit, Vermiculit, Ledikit, Magadit, lllit, Kaolinit, Wollastonit, Attapulgit. Preferred fillers are calcium carbonate, silicates, talc, mica, kaolin, metal oxides and metal hydroxides, carbon black, graphite, wood flour or fibers from natural products such as cellulose. Other suitable fillers are hydrotalcites or zeolites or phyllosilicates such as montmorillonite, bentonite, beidelite, mica, hectorite, saponite, vermiculite, ledikite, magadite, illite, kaolinite, wollastonite, attapulgite.
Geeignete sekundäre Antioxidantien sind insbesondere Phosphite oder Phos- phonite wie z.B. Suitable secondary antioxidants are in particular phosphites or phosphonites such as e.g.
Triphenylphosphit, Diphenylalkylphosphite, Phenyldialkylphosphite, Tri(nonyl- phenyl)phosphit, Trilaurylphosphite, Trioctadecylphosphit, Distearylpenta- erythritoldiphosphit, Tris-(2,4-di-tert-butylphenyl)phosphit, Diisodecylpenta- erythritoldiphosphit, Bis(2,4-di-tert-butylphenyl)pentaerythritoldiphosphit, Bis(2,4-di-cumylphenyl)pentaerythritoldiphosphit, Bis(2,6-di-tert-butyl-4-me- thylphenyl)pentaerythritoldiphosphit, Diisodecyloxypentaerythritoldiphosphit, Bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritoldiphosphit, Bis(2,4,6- tris(tert-butylphenyl)pentaerythritoldiphosphit, Tristearylsorbitoltriphosphit, Tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylendiphosphonit, 6-lsooctyloxy- 2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, Bis(2,4-di- tert-butyl-6-methylphenyl)methylphosphit, Bis(2,4-di-tert-butyl-6-methylphe- nyl)ethylphosphit, 6-Fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]- 1,3,2-dioxaphosphocin, 2,2'2"-Nitrilo[triethyltris(3,3",5,5'-tetra-tert-butyl- 1, 1'-biphenyl-2,2'-diyl)phosphit], 2-Ethylhexyl(3,3',5,5'-tetra-tert-butyl-1, 1'- biphenyl-2,2'-diyl))phosphit, 5-Butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-Triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tri(nonylphenyl) phosphite, trilauryl phosphites, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis(2,4-di-tert -butylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl -6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, 6-isooctyloxy-2 ,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, bis( 2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-Fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3 ,2-dioxaphosphocin, 2,2'2"-nitrilo[triethyltris(3,3",5,5'-tetra-tert -butyl- 1,1'-biphenyl-2,2'-diyl)phosphite], 2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl ))phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-
1,3,2-dioxaphosphiran. 1,3,2-dioxaphosphirane.
Besonders bevorzugte Phosphite sind:
Figure imgf000025_0001
Figure imgf000025_0002
Figure imgf000026_0001
Figure imgf000027_0001
Particularly preferred phosphites are:
Figure imgf000025_0001
Figure imgf000025_0002
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
mit n= 3-100
Figure imgf000028_0001
with n= 3-100
Ein bevorzugtes Phosphonit ist: A preferred phosphonite is:
Figure imgf000029_0001
Figure imgf000029_0001
Geeignete sekundäre Antioxidantien sind weiterhin Organo-Schwefelverbin- dungen wie z.B. Sulfide und Disulfide z.B. Distearylthiodipropionat, Dilau- rylthiodipropionat, Ditridecyldithiopropionat, Ditetradecylthiodipropionat, 3- (dodecylthio)-, 1, 1'-[2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]-1,3-pro- pandiyl]propansäureester. Bevorzugt sind die folgenden Strukturen:
Figure imgf000029_0002
Figure imgf000029_0003
Suitable secondary antioxidants are also organo-sulphur compounds such as sulfides and disulfides, for example distearyl thiodipropionate, dilauryl thiodipropionate, ditridecyldithiopropionate, ditetradecyl thiodipropionate, 3-(dodecylthio)-, 1,1'-[2,2-bis[[3-(dodecylthio). )-1-oxopropoxy]methyl]-1,3-propanediyl]propanoic acid ester. The following structures are preferred:
Figure imgf000029_0002
Figure imgf000029_0003
Geeignete Säurefänger („Antiacids") sind Salze von ein, zwei, drei oder vierwer- tigen Metallen, vorzugsweise Alkali-, Erdalkalimetalle, Aluminium oder Zink, insbesondere gebildet mit Fettsäuren, wie z.B. Calciumstearat, Magnesiumste- arat, Zinkstearat, Aluminiumstearat, Calciumlaurat, Calciumbehenat, Calcium- lactat, Calciumstearoyl-2-lactat. Weitere Klassen geeigneter Säurefänger sind Hydrotalcite, insbesondere synthetische Hydrotalcite auf Aluminium-, Magne- sium- und Zinkbasis, Hydrocalumite, Zeolithe, Erdalkalioxide, insbesondere Cal- ciumoxid und Magnesiumoxid sowie Zinkoxid, Erdalkalicarbonate, insbeson- dere Calciumcarbonat, Magnesiumcarbonat und Dolomit, und Hydroxide, ins- besondere Brucit (Magnesiumhydroxid), Suitable acid scavengers ("antacids") are salts of mono, di, tri or tetravalent metals, preferably alkali metals, alkaline earth metals, aluminum or zinc, formed in particular with fatty acids, such as calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, calcium laurate, Calcium behenate, calcium lactate, calcium stearoyl-2-lactate Other classes of suitable acid scavengers are hydrotalcites, in particular synthetic hydrotalcites based on aluminium, magnesium and zinc, hydrocalumites, zeolites, alkaline earth metal oxides, in particular calcium oxide and magnesium oxide as well as zinc oxide, alkaline earth metal carbonates, in particular calcium carbonate, magnesium carbonate and dolomite, and hydroxides, in particular brucite (magnesium hydroxide),
Geeignete Costabilisatoren sind weiterhin Polyole insbesondere Alditole oder Cyclitole. Polyole sind z.B. Pentaerythrit, Dipentaerythrit, Tripentaerythrit, kurzkettige Polyetherpolyole oder Polyesterpolyole, sowie hyperverzweigte Polymere/Oligomere oder Dendrimere mit Alkoholgruppen z.B.
Figure imgf000030_0001
Suitable co-stabilizers are also polyols, in particular alditols or cyclitols. Polyols are, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, short-chain polyether polyols or polyester polyols, as well as hyperbranched polymers/oligomers or dendrimers with alcohol groups, for example
Figure imgf000030_0001
Vorzugsweise wird das mindestens eine Alditol ausgewählt aus der Gruppe be- stehend ausThreit, Erythrit, Galactit, Mannit, Ribit, Sorbit, Xylit, Arabit, Isomalt, Lactit, Maltit, Altritol, Iditol, Maltotritol und hydrierte Oligo- und Polysaccha- ride mit Polyol-Endgruppen und Mischungen hiervon. Besonders bevorzugt ist das mindestens eine bevorzugte Alditol ausgewählt aus der Gruppe bestehend aus Erythrit, Mannit, Isomalt, Maltit und Mischungen hiervon. The at least one alditol is preferably selected from the group consisting of threitol, erythritol, galactitol, mannitol, ribitol, sorbitol, xylitol, arabitol, isomalt, lactitol, maltitol, altritol, iditol, maltotritol and hydrogenated oligo- and polysaccharides with polyol - end groups and mixtures thereof. The at least one preferred alditol is particularly preferably selected from the group consisting of erythritol, mannitol, isomalt, maltitol and mixtures thereof.
Beispiele für weitere geeignete Zuckeralkohole sind Heptitole und Octitole: meso-glycero-allo-Heptitol, D-glycero-D-altro-Heptitol, D-glycero-D-manno- Heptitol, meso-glycero-gulo-Heptitol, D-glycero-D-galacto-Heptitol (Perseitol), D-glycero-D-gluco-Heptitol, L-glycero-D-gluco Heptitol, D-erythro-L-galacto- Octitol, D-threo-L-galacto-Octitol. Examples of other suitable sugar alcohols are heptitols and octitols: meso-glycero-allo-heptitol, D-glycero-D-altro-heptitol, D-glycero-D-manno-heptitol, meso-glycero-gulo-heptitol, D-glycero- D-galacto-heptitol (perseitol), D-glycero-D-gluco-heptitol, L-glycero-D-gluco-heptitol, D-erythro-L-galacto-octitol, D-threo-L-galacto-octitol.
Insbesondere kann das mindestens eine Cyclitol ausgewählt sein aus der Gruppe bestehend aus Inositol (myo, scyllo-, D-chiro-, L-chiro-, muco-, neo-, allo-, epi- und cis-lnosit), 1,2,3,4-tetrahydroxycyclohexan, 1, 2,3,4, 5-pentahyd- roxycyclohexan, Quercitol, Viscumitol, Bornesitol, Conduritol, Ononitol, Pinitol, Pinpollitol, Quebrachitol, Ciceritol, Chinasäure, Shikimisäure und Valienol, be- vorzugt ist dabei myo-lnosit (myo-lnositol). In particular, the at least one cyclitol may be selected from the group consisting of inositol (myo, scyllo-, D-chiro-, L-chiro-, muco-, neo-, allo-, epi- and cis-inositol), 1,2 ,3,4-tetrahydroxycyclohexane, 1,2,3,4,5-pentahydroxycyclohexane, Quercitol, Viscumitol, Bornesitol, Conduritol, Ononitol, Pinitol, Pinpollitol, quebrachitol, ciceritol, quinic acid, shikimic acid and valienol, preference being given to myo-inositol (myo-inositol).
Geeignete Lichtstabilisatoren sind beispielsweise Verbindungen auf der Basis von 2-(2'-Hydroxyphenyl)benzotriazolen, 2-Hydroxybenzophenonen, Estern von Benzoesäuren, Acrylaten, Oxamiden und 2-(2-Hydroxyphenyl)-1,3,5-Triazi- nen. Examples of suitable light stabilizers are compounds based on 2-(2'-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, esters of benzoic acids, acrylates, oxamides and 2-(2-hydroxyphenyl)-1,3,5-triazines.
Geeignete 2-(2'-Hydroxyphenyl)benzotriazole sind beispielsweise 2-(2'-Hyd- roxy-5'methylphenyl)benzotriazol, 2-(3',5'-Di-tert-butyl-2'-hydroxyphenyl)- benzotriazol, 2-(5'-tert-Butyl-2'-hydroxy-phenyl)benzotriazol, 2-(2'-Hydroxy-5'- (1,1,3,3-tetramethylbutyl)phenyl)benzotriazol, 2-(3',5'-Di-tert-butyl-2'-hydro- xyphenyl)-5-chlorobenzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5'-methylphenyl-5- chlorobenzotriazol, 2-(3'-sec-Butyl-5'-tert-butyl-2'-hydroxy-phenyl)benzotria- zol, 2-(2'-Hydroxy-4'-octyloxyphenyl)benzotriazol, 2-(3',5'-Di-tert-amyl-2'-hyd- roxyphenyl)benzotriazol, 2-(3',5'-Bis(a,a-dimethylbenzyl)-2'-hydroxyphe- nyl)benzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phe- nyl)-5-chlorobenzotriazol, 2-(3'-tert-Butyl-5'-[2-(2-ethylhexyloxy)carbonyl- ethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5'- (2-methoxycarbonyl-ethyl)phenyl)-5-chlorobenzotriazol, 2-(3'-tert-Butyl-2'- hydroxy-5'-(2-methoxycarbony-lethyl)phenyl)-benzotriazol, 2-(3'-tert-Butyl-2'- hydroxy-5'-(2-octyloxycarbonylethyl)-phenyl)-benzotriazol, 2-(3'-tert-Butyl-5'- [2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazol, 2-(3'-Dode- cyl-2'-hydroxy-5'-methylphenyl)benzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5'-(2- isooctyloxycarbonylethyl)-phenyl-benzotriazol, 2,2'-Methylenbis[4-(1,1,3,3- tetramethylbutyl)-6-benzotriazol-2-ylphenol]; das Produkt der Umesterung von 2-[3'-tert-Butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-ben- zotriazol mit Polyethylenglycol 300; [R— CH2CH2— COO— CH2CH2]2, wobei R = 3'-tert-Butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2-[2'-Hydroxy-3'-(α,α- dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)phenyl]-benzotriazol, 2-[2'-hyd- roxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(a,a-dimethylbenzyl)phenyl]benzotria- zoL Examples of suitable 2-(2'-hydroxyphenyl)benzotriazoles are 2-(2'-hydroxy-5'methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole , 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3 ',5'-Di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl-5-chlorobenzotriazole, 2-( 3'-sec-butyl-5'-tert-butyl-2'-hydroxy-phenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di -tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis(a,a-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl -2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonyl-ethyl]-2 '-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonyl-ethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl -2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-benzotriazole, 2-(3'-t tert-Butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)-phenyl)-benzotriazole, 2-(3'-tert-Butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'- hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)- phenyl-benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; the transesterification product of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; [R- CH 2 CH 2 - COO- CH 2 CH 2 ] 2 where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2-[2'-hydroxy -3'-(α,α-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)phenyl]-benzotriazole, 2-[2'-hydroxy-3'-(1,1,3 ,3-tetramethylbutyl)-5'-(a,a-dimethylbenzyl)phenyl]benzotriazole
Geeignete 2-Hydroxybenzophenone sind beispielsweise 4-Hydroxy-, 4-Me- thoxy-, 4-Octyloxy-, 4-Decyloxy- 4-Dodecyloxy, 4-Benzyloxy, 4,2',4'-Trihydroxy- und 2'-Hydroxy-4,4'-dimethyoxy-Derivate der 2-Hydroxybenzophenone. Geeignete Acrylate sind beispielsweise Ethyl-α-cyano-β,β-diphenylacrylat, lsooctyl-α-cyano-β,β-diphenylacrylat, Methyl-α-carbomethoxycinnamat, Me- thyl-α-cyano-β-methyl-p-methoxycinnamat, Butyl-α-cyano-β-methyl-p-me- thoxycinnamat, Methyl-α-carbomethoxy-p-methoxycinnamat und N-(β-carbo- methoxy-β-cyanovinyl)-2-methylindolin. Examples of suitable 2-hydroxybenzophenones are 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy -4,4'-dimethyloxy derivatives of 2-hydroxybenzophenones. Examples of suitable acrylates are ethyl α-cyano-β,β-diphenyl acrylate, isooctyl α-cyano-β,β-diphenyl acrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate and N-(β-carbo-methoxy-β-cyanovinyl)-2-methylindoline.
Geeignete Ester von Benzoesäuren sind beispielsweise 4-tert-Butylphenylsa- licylat, Phenylsalicylat, Octylphenylsalicylat, Dibenzoylresorcinol, Bis(4-tert- butylbenzoyl)resorcinol, Benzoylresorcinol, 2,4-Di-tert-butylphenyl-3,5-di-tert- butyl-4-hydroxybenzoat, Hexadecyl-3,5-di-tert-butyl-4-hydroxy-benzoat, Octa- decyl-3,5-di-tert-butyl-4-hydroxybenzoat, 2-Methyl-4,6-di-tert-butylphenyl- 3,5-di-tert-butyl-4-hydroxybenzoat. Examples of suitable esters of benzoic acids are 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl-3,5-di-tert- butyl 4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxy-benzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6- di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
Geeignete Oxamide sind beispielsweise 4,4'-Dioctyloxyoxanilid, 2,2'-diethoxy- oxanilid, 2,2'-Dioctyloxy-5,5'-di-tert-butoxanilid, 2,2'-didodecyloxy-5,5'-di-tert- butoxanilid, 2-Ethoxy-2'-ethyloxanilid, N,N'-Bis(3-dimethylaminopropyl)oxa- mid, 2-Ethoxy-5-tert-butyl-2'-ethoxanilid und seine Mischungen mit 2-Ethoxy- 2'-ethyl-5,4'-di-tert-butoxanilid, Mischungen von o- und p-Methoxy-disubstitu- ierten Oxaniliden und Mischungen von o- und p-Ethoxy-disubstituierten Oxani- liden. Examples of suitable oxamides are 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'- di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixtures with 2- ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
Geeignete 2-(2-Hydroxyphenyl)-1,3,5-Triazine sind beispielsweise 2,4,6-Tris(2- hydroxy-4-octyloxyphenyl)-1,3,5-triazin, 2-(2-Hydroxy-4-octyloxyphenyl)-4,6- bis(2,4-dimethylphenyl)-1,3,5-triazin, 2-(2,4-Dihydroxyphenyl)-4,6-bis(2,4-di- methylphenyl)-1,3,5-triazin, 2,4-Bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-di- methylphenyl)-1,3,5-triazin, 2-(2-Hydroxy-4-octyloxyphenyl)-4,6-bis(4-methyl- phenyl-1,3,5-triazin, 2-(2-Hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethyl- phenyl)-1,3,5-triazin, 2-(2-Hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethyl- phenyl)-1,3,5-triazin, 2-[2-Hydroxy-4-(2-hydroxy-3-butyloxypropoxy)-phenyl]- 4,6-bis(2,4-dimethyl)-1,3,5-triazin, 2-[2-Hydroxy-4-(2-hydroxy-3-octyloxypro- pyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazin, 2-[4-(Dodecyloxy/Tridecy- loxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5- triazin, 2-[2-Hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4- dimethylphenyl-1,3,5-triazin, 2-(2-Hydroxy-4-hexyloxy)phenyl-4,6-diphenyl- 1,3,5-triazin, 2-(2-Hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazin, 2,4,6- Tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazin, 2-(2-Hyd- roxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazin, 2-{2-Hydroxy-4-[3-(2- ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl- 1,3,5-triazin. Examples of suitable 2-(2-hydroxyphenyl)-1,3,5-triazines are 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy- 4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy -4-octyloxyphenyl)-4,6-bis(4-methyl- phenyl-1,3,5-triazine, 2-(2-Hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethyl- phenyl)-1,3,5-triazine, 2-(2-Hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2 -Hydroxy-4-(2-hydroxy-3-butyloxypropoxy)-phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-Hydroxy-4-(2 -hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)- 2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6 -bis(2,4-dimethylphenyl-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphe nyl-1,3,5-triazine, 2-(2-Hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6- Tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl- 1,3,5-triazine, 2-{2-Hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl- 1 ,3,5-triazine.
Geeignete Metalldeaktivatoren sind beispielsweise N,N'-Diphenyloxamid, N- Salicylal-N'-salicyloylhydrazin, N,N'-Bis(salicyloyl)hydrazin, N,N'-Bis(3,5-di-tert- butyl-4-hydroxy-phenyl-propionyl)hydrazin, 3-Salicyloylamino-1,2,4-triazol, Bis(benzyliden)oxalyldihydrazid, Oxanilid, Isophthaloyldihydrazid, Sebacoylbis- phenylhydrazid, N,N'-Diacetyladipoyldihydrazid, N,N'-Bis(salicyloyl)oxylyldi- hydrazid, N,N'-Bis(salicyloyl)thiopropionyldihydrazid. Examples of suitable metal deactivators are N,N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4- hydroxy-phenyl-propionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacoylbis- phenylhydrazide, N,N'-diacetyladipoyldihydrazide, N,N'-bis(salicyloyl) oxylyldihydrazide, N,N'-bis(salicyloyl)thiopropionyldihydrazide.
Besonders bevorzugt als Metalldeaktivatoren sind:
Figure imgf000033_0001
Particularly preferred as metal deactivators are:
Figure imgf000033_0001
Geeignete niedermolekulare gehinderte Amine sind beispielsweise 1,1-Bis(2,2,6,6-tetramethyl-4-piperidyl)succinat, Bis(1, 2,2,6, 6-pentamethyl- 4-piperidyl)sebazat, Bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebazat, Bis(1, 2,2,6, 6-pentamethyl-4-piperidyl)-n-butyl-3,5-di-tert-butyl-4-hydroxy- benzylmalonat, das Kondensationsprodukt aus 1-(2-Hydroxyethyl)-2, 2,6,6- tetramethyl-4-hydroxypiperidin und Succinsäure, lineare oder zyklische Kon- densationsprodukte von N,N'-Bis(2 ,2,6,6-tetramethyl-4-piperidyl )hexame- thylendiamin und 4-tert-Octylamino-2,6-di-chloro-1,3,5-triazin, Tris(2, 2,6,6- tetramethyl-4-piperidyl)nitrilotriacetat, Tetrakis(2,2,6,6-tetra-methyl-4-pipe- ridyl)-1,2,3,4-butantetracarboxylat, 1, 1'-(1,2-Ethandiyl)-bis(3,3,5,5-tetrame- thylpiperazinon), 4-Benzoyl-2,2,6,6-tetramethylpiperidin oder 4-Stearyloxy- 2,2,6,6-tetramethylpiperidin. Examples of suitable low molecular weight hindered amines are 1,1-bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebazate, bis( 1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebazate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-n-butyl-3,5-di-tert -butyl-4-hydroxy-benzylmalonate, the condensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N,N'-bis( 2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6- tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetra-methyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, 1,1'-(1,2-ethanediyl )-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine or 4-stearyloxy- 2,2,6,6-tetramethylpiperidine.
Umfasst in den oben angegebenen Strukturen sind dabei jeweils auch die ste- risch gehinderten N-H, N-alkyl wie N-methyl oder N-octyl, die N-alkoxy-Deri- vate wie N-methoxy oder N-octyloxy, die Cycloalkylderivate wie N-cyclohexy- loxy und die N-(2-hydroxy-2-methylpropoxy) Analoga. The structures given above also include the sterically hindered N-H, N-alkyl such as N-methyl or N-octyl, the N-alkoxy derivatives such as N-methoxy or N-octyloxy, the cycloalkyl derivatives such as N -cyclohexyloxy and the N-(2-hydroxy-2-methylpropoxy) analogs.
Bevorzugte niedermolekulare gehinderte Amine weisen weiterhin die folgen- den Strukturen auf:
Figure imgf000034_0001
Figure imgf000034_0002
Figure imgf000035_0001
Figure imgf000036_0001
Preferred low molecular weight hindered amines also have the following structures:
Figure imgf000034_0001
Figure imgf000034_0002
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000037_0001
Bevorzugte oligomere oder polymere gehinderte Amine sind:
Figure imgf000037_0002
Figure imgf000038_0001
Preferred oligomeric or polymeric hindered amines are:
Figure imgf000037_0002
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000039_0001
Bei den zuvor genannten Verbindungen bedeutet n jeweils 3 bis 100. In the compounds mentioned above, n is in each case from 3 to 100.
Ein weiterer geeigneter Lichtstabilisator ist Hostanox NOW (Hersteller: Clari- ant SE) mit der folgenden allgemeinen Struktur:
Figure imgf000039_0002
wobei R -O-C(O)-C15H31 oder -O-C(O)-C17H35 bedeutet. Umfasst in den oben angegebenen Strukturen sind dabei jeweils auch die ste- risch gehinderten N-H, N-alkyl wie N-methyl oder N-octyl, die N -alkoxy- Deri- vate wie N-methoxy oder N-octyloxy, die Cycloalkylderivate wie N-cyclohexy- loxy und die N-(2-hydroxy-2-methylpropoxy) Analoga. Another suitable light stabilizer is Hostanox NOW (manufacturer: Clariant SE) with the following general structure:
Figure imgf000039_0002
where R is -OC(O)-C 15 H 31 or -OC(O)-C 17 H 35 . The structures given above also include the sterically hindered NH, N-alkyl such as N-methyl or N-octyl, the N-alkoxy derivatives such as N-methoxy or N-octyloxy, the cycloalkyl derivatives such as N -cyclohexyloxy and the N-(2-hydroxy-2-methylpropoxy) analogs.
Geeignete Dispergiermittel sind beispielsweise: Examples of suitable dispersing agents are:
Polyacrylate, z.B. Copolymere mit langkettigen Seitengruppen, Polyacrylat- Blockcopolymere, Alkylamide: z.B. N,N'-1,2-Ethandiylbisoctadecanamid Sorbi- tanester, z.B. Monostearylsorbitanester, Titanate und Zirconate, reaktive Co- polymere mit funktionellen Gruppen z.B. Polypropylen-co-Acrylsäure, Polypro- pylen-co-Maleinsäureanhydrid, Polyethylen-co-Glycidylmethacrylat, Polysty- rol-alt-Maleinsäureanhydrid-Polysiloxane: z.B. Dimethylsilandiol-Ethylenoxid Copolymer, Polyphenylsiloxan Copolymer, Amphiphile Copolymere: z.B. Poly- ethylen-block-Polyethylenoxid, Dendrimere, z.B. hydroxylgruppenhaltige Den- drimere. Polyacrylates, e.g., copolymers with long-chain side groups, polyacrylate block copolymers, alkylamides: e.g., N,N'-1,2-ethanediylbisoctadecanamide sorbitan esters, e.g., monostearyl sorbitan esters, titanates and zirconates, reactive copolymers with functional groups, e.g., polypropylene-co-acrylic acid, Polypropylene-co-maleic anhydride, polyethylene-co-glycidyl methacrylate, polystyrene-alt-maleic anhydride-polysiloxanes: e.g. dimethylsilanediol-ethylene oxide copolymer, polyphenylsiloxane copolymer, amphiphilic copolymers: e.g. polyethylene block polyethylene oxide, dendrimers, e.g. den - drimmer.
Geeignete Antinukleierungsmittel sind Azinfarbstoffe wie z.B. Nigrosin. Suitable antinucleating agents are azine dyes such as nigrosine.
Geeignete Flammschutzmittel sind insbesondere a) Anorganische Flammschutzmittel wie z.B. AI(OH)3, Mg(OH)2, AIO(OH), MgCO3, Schichtsilikate wie z.B. Montmorillonit oder Sepiolit, nicht oder organisch modifiziert, Doppelsalze, wie z.B. Mg-Al-Silikate, POSS-(Po- lyhedral Oligomeric Silsesquioxane) Verbindungen, Huntit, Hydromagne- sit oder Halloysit sowie Sb2O3, Sb2O5, MoO3, Zinkstannat, Zinkhydroxyst- annat, b) Stickstoffhaltige Flammschutzmittel wie z.B. Melamin, Melem, Melam, Melon, Melaminderivate, Melaminkondensationsprodukte oder Mela- minsalze, Benzoguanamin, Po lyisocyan urate, Allantoin, Phosphacene, insbesondere Melamincyanurat, Melaminphosphat, Dimelaminphos- phat, Melaminpyrophosphat, Melaminpolyphosphat, Melamin-Metall- Phosphate wie z.B. Melaminaluminiumphosphat, Melaminzinkphosphat, Melaminmagnesiumphosphat, sowie die entsprechenden Pyrophosphate und Polyphosphate, Poly-[2,4-(piperazin-1,4-yl)-6-(morpholin-4-yl)-1,3,5- triazin], Ammonium-polyphosphat, Melaminborat, Melaminhydrobro- mid, c) Radikalbildner, wie z.B. Alkoxyamine, Hydroxylaminester, Azoverbindun- gen, Sulfenamide, Sulfenimide, Dicumyl oder Polycumyl, Hydroxyimide und deren Derivate wie z.B. Hydroxyimidester oder Hydroxyimidether d) Phosphorhaltige Flammschutzmitteln wie z.B. roter Phosphor, Phosphate wie z.B. Resorcindiphosphat, Bisphenol-A-diphosphat und ihre Oligo- mere, Triphenylphosphat, Ethylendiamindiphosphat, Phosphinate wie z.B. Salze der hypophosphorigen Säure und Ihrer Derivate wie Alkylphos- phinatsalzen z.B. Diethylphosphinataluminium oder Diethylphosphinat- Zink oder Aluminiumphosphinat, Aluminiumphosphit, Aluminiumphos- phonat, Phosphonatester, oligomere und polymere Derivate der Methan- phosphonsäure, 9,10-Dihydro-9-oxa-10-phosphorylphenanthren-10-oxid (DOPO) und deren substituierte Verbindungen, e) Halogenhaltige Flammschutzmittel auf Chlor- und Brombasis wie z.B. po- lybrominierte Diphenyloxide, wie z.B. Decabromdiphenyloxid, Tris(3- bromo-2,2-bis(bromomethyl)propyl-phosphat, Tris(tribromneopen- tyl)phosphat, Tetrabromphthalsäure, 1,2-Bis(tribromphenoxy)ethan, He- xabromcyclododecan, bromiertes Diphenylethan, Tris-(2,3-dibrompro- pyl)isocyanurat, Ethylen-bis(tetrabromophthalimid), Tetrabromo-bi- sphenol A, bromiertes Polystyrol, bromiertes Polybutadien bzw, Polysty- rol-bromiertes Polybutadien-Copolymere, bromierter Polyphenylenther, bromiertes Epoxidharz, Polypentabrombenzylacrylat, ggf. in Kombination mit Sb2O3 und/oder Sb2O5, f) Borate wie z.B. Zinkborat oder Calciumborat, ggf. auf Trägermaterial wie z.B. Silica g) Schwefelhaltige Verbindungen wie z.B. elementarer Schwefel, Disulfide und Polysulfide, Thiuramsulfid, Dithiocarbamate, Mercaptobenzthiazol und Sulfenamide, h) Antidrip-Mitteln wie z.B. Polytetrafluorethylen, i) Siliciumhaltige Verbindungen wie z.B. Polyphenylsiloxane, j) Kohlenstoffmodifikationen wie z.B. Carbon-Nanoröhren (CNT), Blähgra- phit oder Graphen k) sowie Kombinationen oder Mischungen hieraus. Suitable flame retardants are in particular a) Inorganic flame retardants such as Al(OH) 3 , Mg(OH) 2 , AlO(OH), MgCO 3 , phyllosilicates such as montmorillonite or sepiolite, unmodified or organically modified, double salts such as Mg-Al- Silicates, POSS (polyhedral oligomeric silsesquioxane) compounds, huntite, hydromagnesite or halloysite as well as Sb 2 O 3 , Sb 2 O 5 , MoO 3 , zinc stannate, zinc hydroxystannate, b) nitrogen-containing flame retardants such as melamine, melem, Melam, melon, melamine derivatives, melamine condensation products or melamine salts, benzoguanamine, polyisocyanurate, allantoin, phosphacene, in particular melamine cyanurate, melamine phosphate, dimelamin phosphate, melamine pyrophosphate, melamine polyphosphate, melamine metal phosphates such as melamine aluminum phosphate, melamine zinc phosphate, melamine magnesium phosphate, and the corresponding pyrophosphates and polyphosphates, poly-[2,4-(piperazin-1,4-yl)-6-(morpholin-4-yl)-1,3,5- triazine], ammonium polyphosphate, melamine borate, melamine hydrobromide mid, c) radical formers such as alkoxyamines, hydroxylamine esters, azo compounds, sulfenamides, sulfenimides, dicumyl or polycumyl, hydroxyimides and their derivatives such as hydroxyimide esters or hydroxyimide ethers d) phosphorus-containing flame retardants such as Red phosphorus, phosphates such as resorcinol diphosphate, bisphenol A diphosphate and their oligomers, triphenyl phosphate, ethylene diamine diphosphate, phosphinates such as salts of hypophosphorous acid and their derivatives such as alkyl phosphinate salts such as diethyl phosphinate aluminum or diethyl phosphinate zinc or aluminum phosphinate, aluminum phosphite, aluminum phosphite phonate, phosphonate esters, oligomeric and polymeric derivatives of methanephosphonic acid, 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO) and their substituted compounds, e) halogen-containing flame retardants based on chlorine and bromine, such as po - Lybrominated diphenyl oxides, such as decabromodiphenyl oxide, tris(3-br omo-2,2-bis(bromomethyl)propyl phosphate, tris(tribromoneopentyl) phosphate, tetrabromophthalic acid, 1,2-bis(tribromophenoxy)ethane, hexabromocyclododecane, brominated diphenylethane, tris-(2,3-dibromopro- pyl)isocyanurate, ethylene bis(tetrabromophthalimide), tetrabromobisphenol A, brominated polystyrene, brominated polybutadiene or polystyrene-brominated polybutadiene copolymers, brominated polyphenylene ether, brominated epoxy resin, polypentabromobenzyl acrylate, possibly in combination with Sb 2 O 3 and/or Sb 2 O 5 , f) borates such as zinc borate or calcium borate, optionally on a carrier material such as silica g) sulfur-containing compounds such as elemental sulfur, disulfides and polysulfides, thiuram sulfide, dithiocarbamates, mercaptobenzothiazole and sulfenamides, h) antidrip Agents such as polytetrafluoroethylene, i) silicon-containing compounds such as polyphenylsiloxanes, j) carbon modifications such as carbon nanotubes (CNT), expandable graphite or graphene k) and combinations or mixtures thereof.
Geeignete Weichmacher sind beispielsweise Phthalsäureester, Adipinsäurees- ter, Ester der Zitronensäure, Ester der 1,2-Cyclohexandicarbonsäure, Trimel- lithsäureester, Isosorbidester, Phosphatester, Epoxide wie z.B. epoxidiertes So- jabohnenöl oder aliphatische Polyester. Examples of suitable plasticizers are phthalic acid esters, adipic acid esters, citric acid esters, 1,2-cyclohexanedicarboxylic acid esters, trimellitic acid esters, isosorbide esters, phosphate esters, epoxides such as epoxidized soybean oil or aliphatic polyesters.
Geeignete Gleitmittel und Verarbeitungshilfsmittel sind beispielsweise Po- lyethylenwachse, Polypropylenwachse, Salze von Fettsäuren wie z.B. Calci- umstearat, Zinkstearat oder Salze von Montanwachsen, Amidwachse wie z.B. Erucasäureamid oder Ölsäureamide, Fluorpolymere, Silikone oder Neoalkoxy- titanate- und Zirkonate. Suitable lubricants and processing aids are, for example, polyethylene waxes, polypropylene waxes, salts of fatty acids such as calcium stearate, zinc stearate or salts of montan waxes, amide waxes such as erucic acid amide or oleic acid amides, fluoropolymers, silicones or neoalkoxy titanate and zirconates.
Geeignete Pigmente können anorganischer oder organischer Natur sein. Anor- ganische Pigmente sind beispielsweise Titandioxid, Zinkoxid, Zinksulfid, Eisen- oxid, Ultramarin, Ruß, organische Pigmente sind beispielsweise Anthrachinone, Anthanthrone, Benzimidazolone, Chinacridone, Diketopyrrolopyrrole, Dio- xazine, Indanthrone, Isoindolinone, Azo-Verbindungen, Perylene, Phthalocya- nine oder Pyranthrone. Weitere geeignete Pigmente sind Effektpigmente auf Metallbasis oder Perlglanzpigmente auf Metalloxid-Basis. Suitable pigments can be inorganic or organic in nature. Inorganic pigments are, for example, titanium dioxide, zinc oxide, zinc sulfide, iron oxide, ultramarine, carbon black, organic pigments are, for example, anthraquinones, anthanthrones, benzimidazolones, quinacridones, diketopyrrolopyrroles, dioxazines, indanthrones, isoindolinones, azo compounds, perylenes, phthalocyanines nine or pyranthrones. Other suitable pigments are metal-based effect pigments or metal-oxide-based pearlescent pigments.
Geeignete Optische Aufheller sind beispielsweise Bisbenzoxazole, Phenylcuma- rine oder Bis(styryl)biphenyle und insbesondere optische Aufheller der For- meln: Suitable optical brighteners are, for example, bisbenzoxazoles, phenylcoumarins or bis(styryl)biphenyls and in particular optical brighteners of the formulas:
Figure imgf000043_0001
Figure imgf000043_0001
Geeignete Füllstoffdeaktivatoren sind beispielsweise Polysiloxane, Polyacrylate insbesondere Blockcopolymere wie Polymethacrylsäure-polyalkylenoxid oder Polyglycidyl(meth)acrylate und deren Copolymere z.B. mit Styrol sowie Epoxide z.B. der folgenden Strukturen:
Figure imgf000043_0002
Suitable filler deactivators are, for example, polysiloxanes, polyacrylates, in particular block copolymers such as polymethacrylic acid-polyalkylene oxide or polyglycidyl (meth)acrylates and their copolymers, for example with styrene, and epoxides, for example of the following structures:
Figure imgf000043_0002
Figure imgf000044_0001
Figure imgf000044_0001
Geeignete Antistatika sind beispielsweise ethoxylierte Alkylamine, Fettsäurees- ter, Alkylsulfonate und Polymere wie z.B. Polyetheramide. Examples of suitable antistatic agents are ethoxylated alkylamines, fatty acid esters, alkylsulfonates and polymers such as polyetheramides.
Geeignete Antiozonantien sind die oben genannten Amine wie z.B. N,N'-Di- isopropyl-p-phenylendiamin, N,N'-Di-sec-butyl-p-phenylendiamin, N,N'- Bis(1,4-dimethylpentyl)-p-phenylendiamin, N,N'-Dicyclohexyl-p-phenylendia- min, N-lsopropyl-N'-phenyl-p-phenylendiamin, N-(1,3-Dimethylbutyl)-N'-phe- nyl-p-phenylen-diamin, N-(1-Methylheptyl)-N'-phenyl-p-phenylendiamin, N- Cyclohexyl-N'-phenyl-p-phenylendiamin. Suitable antiozonants are the amines mentioned above, such as N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl) -p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenedi- min, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl -p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine.
Geeignete Nukleierungsmittel sind Talkum, Alkali oder Erdalkalisalze von mono- und polyfunktionellen Carbonsäuren wie z. B. Benzoesäure, Bern- steinsäure, Adipinsäure, z.B. Natriumbenzoat, Zinkglycerolat, Alumi- niumhydroxy-bis(4-tert-butyl)benzoat, 2,2'-Methylen-bis-(4,6-di-tert-butyl- phenyl)phosphat, sowie Trisamide und Diamide wie z.B. Trimesinsäuretricyclo- hexylamid, Trimesinsäuretri(4-methylcyclohexylamid), Trimesinsäure tri(tert.butylamid), N,N',N"-1,3,5-Benzoltriyltris(2,2-dimethyl-propanamid) oder 2,6-Naphthalindicarbosäuredicyclohexylamid. Suitable nucleating agents are talc, alkali metal or alkaline earth metal salts of mono- and polyfunctional carboxylic acids such as. benzoic acid, succinic acid, adipic acid, e.g ) phosphate, as well as trisamides and diamides such as e.g. propanamide) or 2,6-naphthalene dicarboxylic acid dicyclohexylamide.
Geeignete Additive zum Molekulargewichtsaufbau von Polykondensationspo- lymeren (Kettenverlängerer) sind Diepoxide, Bis-Oxazoline, Bis-Oxazolone, Bis- Oxazine, Diisocyanate, Dianhydride, Bis-Acyllactame, Bis-Maleimide, Dicya- nate, Carbodiimide. Weitere geeignete Kettenverlängerer sind polymere Ver- bindungen wie z.B. Polystyrol-Polyacrylat-Polyglycidyl(meth)acrylat- Copoly- mere, Polystyrol-Maleinsäureanhydrid-Copolymere und Polyethylen-Malein- säureanhydrid-Copolymere. Suitable additives for increasing the molecular weight of polycondensation polymers (chain extenders) are diepoxides, bis-oxazolines, bis-oxazolones, bis-oxazines, diisocyanates, dianhydrides, bis-acyllactams, bis-maleimides, dicyanates, carbodiimides. Other suitable chain extenders are polymeric compounds such as, for example, polystyrene-polyacrylate-polyglycidyl (meth)acrylate copolymers, polystyrene-maleic anhydride copolymers and polyethylene-maleic anhydride copolymers.
Geeignete Additive zur Erhöhung der elektrischen Leitfähigkeit sind beispiels- weise die erwähnten Antistatika, Ruß und Kohlenstoffverbindungen wie Koh- lenstoff-Nanoröhrchen und Graphen, Metallpulver wie z.B. Kupferpulver und leitfähige Polymere wie bsp. Polypyrrole, Polyaniline und Polythiophene. Geig- nete Additive zur Erhöhung der thermischen Leitfähigkeit sind beispielsweise Aluminumnitride und Bornitride. Suitable additives for increasing the electrical conductivity are, for example, the antistatic agents mentioned, soot and carbon compounds such as carbon nanotubes and graphene, metal powder such as copper powder and conductive polymers such as polypyrroles, polyanilines and polythiophenes. Examples of suitable additives for increasing the thermal conductivity are aluminum nitrides and boron nitrides.
Geeignete Infrarot -aktive Additive sind beispielsweise Aluminumsilikate, Hyd- rotalcite oder Farbstofef wie Phthalocyanine oder Anthrachinone. Examples of suitable infrared-active additives are aluminum silicates, hydrotalcites or dyes such as phthalocyanines or anthraquinones.
Geeignete Entformungshilfsmittel sind beispielsweise Silikone, Seifen und Wachse wie z.B. Montanwachse. Die Einarbeitung der oben beschriebenen Additivzusammensetzung und ggf. der zusätzlichen Additive in den Kunststoff erfolgt durch übliche Verarbeitungs- methoden, wobei das Polymere aufgeschmolzen und mit der erfindungsgemä- ßen Additivzusammensetzung und den ggf. weiteren Zusätzen gemischt wird, vorzugsweise durch Mischer, Kneter oder Extruder. Als Verarbeitungsmaschi- nen bevorzugt sind Extruder wie z.B. Einschneckenextruder, Zweischnecken- extruder, Planetwalzenextruder, Ringextruder, Co-Kneter, die vorzugsweise mit einer Vakuumentgasung ausgestattet sind. Die Verarbeitung kann dabei un- ter Luft oder ggf. unter Inertgasbedingungen erfolgen. Examples of suitable mold release agents are silicones, soaps and waxes such as montan waxes. The additive composition described above and any additional additives are incorporated into the plastic using conventional processing methods, with the polymer being melted and mixed with the additive composition according to the invention and any other additives, preferably using mixers, kneaders or extruders. Preferred processing machines are extruders such as, for example, single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, co-kneaders, which are preferably equipped with vacuum degassing. The processing can take place under air or possibly under inert gas conditions.
Weiterhin können die erfindungsgemäßen Additivzusammensetzungen in Form von sogenannten Masterbatchen oder Konzentraten, die beispielsweise 10-90 % der erfindungsgemäßen Zusammensetzungen in einem Polymeren enthal- ten, hergestellt und eingebracht werden. Furthermore, the additive compositions according to the invention can be produced and introduced in the form of so-called masterbatches or concentrates, which contain, for example, 10-90% of the compositions according to the invention in a polymer.
Des Weiteren betrifft die vorliegende Erfindung ein Formteil bzw. einen Form- körper, der aus einer hydrolysestabilisierten Zusammensetzung gemäß der vor- liegenden Erfindung herstellbar ist. Insbesondere ist das Formteil bzw. der Formkörper ausgewählt aus der Gruppe bestehend aus Folien, Filmen, Schäu- men, Fasern, Kabeln und Rohren, Profilen, Hohlkörpern, Bändchen, Membra- nen, wie z.B. Geomembranen, oder Klebstoffen, die über Extrusion, Spritzguss, Blasformen, Kalandrieren, Pressverfahren, Spinnprozesse, Rotomoulding her- gestellt werden z.B. für die Elektro- und Elektronikindustrie, Bauindustrie, Transportindustrie (Auto, Flugzeug, Schiff, Bahn), für medizinische Anwendun- gen, für Haushalts- und Elektrogeräte, Fahrzeugteile, Konsumartikel, Verpa- ckungen, Möbel, Textilien. Furthermore, the present invention relates to a molded part or a molded body that can be produced from a hydrolysis-stabilized composition according to the present invention. In particular, the molded part or molded body is selected from the group consisting of foils, films, foams, fibers, cables and pipes, profiles, hollow bodies, ribbons, membranes such as geomembranes, or adhesives, which are produced via extrusion, injection molding , blow molding, calendering, pressing processes, spinning processes, rotomoulding, e.g. for the electrical and electronics industry, construction industry, transport industry (car, plane, ship, train), for medical applications, for household and electrical appliances, vehicle parts, consumer goods , packaging, furniture, textiles.
Die vorliegende Erfindung wird anhand der nachfolgenden Beispiele näher erläutert, ohne dass die Beispiele beschränkend für den Gegenstand der vorlie- genden Erfindung zu deuten wären. The present invention is explained in more detail using the examples below, without the examples being interpreted as limiting the subject matter of the present invention.
Ausführungsbeispiele: Examples:
Die folgenden Zusätze wurden bei den Beispielen verwendet: The following additives were used in the examples:
Hydrotalcit 1: Actilox CAH EXP 0213; Lieferant: Fa. Nabaltec Hydrotalcit 2: DHT-4C; Lieferant: Kisuma Chemicals, kalzinierte Version desHydrotalcite 1: Actilox CAH EXP 0213; Supplier: Nabaltec Hydrotalcite 2: DHT-4C; Supplier: Kisuma Chemicals, calcined version of
DHT-4A DHT-4A
Hydrotalcit 3: Hycite 713; Lieferant: Clariant SE Hydrotalcite 3: Hycite 713; Supplier: Clariant SE
Hydrotalcit 4: Sorbacid 911; Lieferant: Clariant SE Hydrotalcite 4: Sorbacid 911; Supplier: Clariant SE
Hydrotalcit 5: DHT-4A; Lieferant: Kisuma Chemicals Hydrotalcite 5: DHT-4A; Supplier: Kisuma Chemicals
Als Zeolith wurde ein Molekularsieb Typ 13X von AlfaAesar verwendet. AlfaAesar type 13X molecular sieve was used as the zeolite.
Bei dem Aziridin handelt es sich um das POLY-U Powder des Herstellers Mena- diona. Die chemische Bezeichnung lautet N,N'-(Methylendi-p-pheny- len)bis(aziridin-1-carboxamid). The aziridine is the POLY-U Powder from the manufacturer Menadiona. The chemical name is N,N'-(methylenedi-p-phenylene)bis(aziridine-1-carboxamide).
Zur Prüfung der Wirkung der erfindungsgemäßen Stabilisatoren-Zusammenset- zung wurde ein Polylactid (PLA) (Luminy L130, Lieferant: Total Corbion) zusam- men mit den in der Tabelle 1 angegebenen Zusätzen bei 200 °C max. in einem Doppelschnecken-Extruder (Process 11, Hersteller ThermoScientific) bei einem Durchsatz von 800 g/h compoundiert. Polymer und Additive wurden vor der Verarbeitung im Vakuumtrockner über Nacht getrocknet. Nach der Compoun- dierung wurden die Compounds bei 60 °C im Wärmeschrank für 2 Wochen (336 Stunden) in entionisiertem Wasser gealtert. Nach der Alterung wurden die Pro- ben über Nacht getrocknet und der MVR bestimmt (190 °C / 2,16 kg). To test the effect of the stabilizer composition according to the invention, a polylactide (PLA) (Luminy L130, supplier: Total Corbion) was tested together with the additives specified in Table 1 at a maximum of 200° C. in a twin-screw extruder (Process 11, manufacturer ThermoScientific) at a throughput of 800 g/h. Polymer and additives were dried overnight in a vacuum dryer before processing. After compounding, the compounds were aged in deionized water at 60 °C in a heating cabinet for 2 weeks (336 hours). After aging, the samples were dried overnight and the MVR determined (190 °C / 2.16 kg).
Tabelle 1: Hydrolysestablität von PLA
Figure imgf000047_0001
Table 1: Hydrolytic stability of PLA
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000048_0001
Zur Prüfung der Wirkung der erfindungsgemäßen Stabilisatoren-Zusammenset- zung wurde ein Polybutylenterephthalat (PBT) (Pocan B1204, Lieferant: Lan- xess) zusammen mit den in derTabelle 2 angegebenen Zusätzen bei 245 °C max. in einem Doppelschnecken-Extruder (Process 11, Hersteller ThermoScientific) bei einem Durchsatz von 800 g/h compoundiert. Polymer und Additive wurden vor der Verarbeitung im Vakuumtrockner über Nacht getrocknet. Nach der Compoundierung wurden die Compounds bei 85 °C im Wärmeschrank für 2 Wochen (336 Stunden) in entionisiertem Wasser gealtert. Nach der Alterung wurden die Proben über Nacht getrocknet und der MVR bestimmt (250 °C / 2,16 kg). To test the effect of the stabilizer composition according to the invention, a polybutylene terephthalate (PBT) (Pocan B1204, supplier: Lanxess) was extruded together with the additives specified in Table 2 at a maximum of 245° C. in a twin-screw extruder (Process 11, manufacturer ThermoScientific) at a throughput of 800 g/h. Polymer and additives were dried overnight in a vacuum dryer before processing. After compounding, the compounds were aged at 85°C in an oven for 2 weeks (336 hours) in deionized water. After aging, the samples were dried overnight and the MVR was determined (250 °C / 2.16 kg).
Tabelle 2: Hydrolysestablität von PBT
Figure imgf000048_0002
Figure imgf000049_0001
Table 2: Hydrolytic stability of PBT
Figure imgf000048_0002
Figure imgf000049_0001
Zur Prüfung der Wirkung der erfindungsgemäßen Stabilisatoren-Zusammenset- zung wurde ein Polyamid 6 (PA6) (Ultramid B27E, Lieferant: BASF) zusammen mit den in der Tabelle 3 angegebenen Zusätzen bei 245 °C max. in einem Mik- rocompounder (Micro 5cc Twin Screw Extruder, Hersteller DSM) compoun- diert. Polymer und Additive wurden vor der Verarbeitung im Vakuumtrockner über Nacht getrocknet. Nach der Compoundierung wurden die Compounds bei 85 °C im Wärmeschrank für 2 Wochen (336 Stunden) in entionisiertem Wasser gealtert. Nach der Alterung wurden die Proben über Nacht getrocknet und das Molekulargewicht mittels GPC bestimmt. To test the effect of the stabilizer composition according to the invention, a polyamide 6 (PA6) (Ultramid B27E, supplier: BASF) was combined with the additives specified in Table 3 at a maximum of 245° C. in a microcompounder (Micro 5cc Twin Screw Extruder, manufacturer DSM) compounded. Polymer and additives were dried overnight in a vacuum dryer before processing. After compounding, the compounds were aged at 85°C in an oven for 2 weeks (336 hours) in deionized water. After aging, the samples were dried overnight and the molecular weight determined by GPC.
Tabelle 3: Hydrolysestablität von PA6
Figure imgf000050_0001
Table 3: Hydrolytic stability of PA6
Figure imgf000050_0001
Der MVR ist ein Maß für das Molekulargewicht des Polymeren. Je höher der MVR, desto niedsriger ist das Molekuargewicht und damit der erfolgte Abbau des Polymeren durch Hydrolyse. Je geringer die MVR-Zunahme desto höher ist die Hydrolysestabilität. Die erfindungsgemäßen Kombinationen zeigen damit eine ausgezeichnete Hydrolysestabilität. The MVR is a measure of the molecular weight of the polymer. The higher the MVR, the lower the molecular weight and thus the degradation of the polymer by hydrolysis that has taken place. The lower the MVR increase, the higher the hydrolytic stability. The combinations according to the invention therefore exhibit excellent hydrolytic stability.

Claims

Patentansprüche patent claims
1. Stabilisator-Zusammensetzung, bestehend aus mindestens einem Aziridin und mindestens einem Hydrotalcit, Zeolith, Dawsonit oder Mischungen hie- raus. 1. Stabilizer composition consisting of at least one aziridine and at least one hydrotalcite, zeolite, dawsonite or mixtures thereof.
2. Stabilisator-Zusammensetzung nach Anspruch 1, dadurch gekennzeich- net, dass das mindestens eine Aziridin ausgewählt ist aus der Gruppe bestehend aus monofunktionellen, difunktionellen, trifunktionellen, tetrafunktionellen und/oder multifunktionellen Aziridinen mit bei- spielsweise den folgenden Strukturen: 2. Stabilizer composition according to claim 1, characterized in that the at least one aziridine is selected from the group consisting of monofunctional, difunctional, trifunctional, tetrafunctional and/or multifunctional aziridines with, for example, the following structures:
A) monofunktionellen Aziridinen A) Monofunctional aziridines
1 -Aziridincarboxamid, N-octadecyl-; 1 -aziridinecarboxamide, N-octadecyl-;
1-Aziridincarboxamid, N-phenyl-; 1-aziridinecarboxamide, N-phenyl-;
1 -Aziridincarboxamid, N-cyclohexyl-; 1 -aziridinecarboxamide, N -cyclohexyl-;
1-Aziridincarboxamid, N-1-naphthalenyl-; 1-aziridinecarboxamide, N-1-naphthalenyl-;
1-Aziridincarboxamid, N-decyl-; 1-aziridinecarboxamide, N-decyl-;
N-Benzyloxycarbonylaziridine; N-benzyloxycarbonylaziridines;
(4-Methoxyphenyl)(2-methyl-1-aziridinyl)methanon; (4-methoxyphenyl)(2-methyl-1-aziridinyl)methanone;
N-(4-Cyclohexylphenyl)-1-aziridincarboxamid; N-(4-cyclohexylphenyl)-1-aziridinecarboxamide;
2-[2-(1-Aziridinyl)ethoxy]-4-pyridincarboxylsäure; 2-[2-(1-Aziridinyl)ethoxy]-4-pyridinecarboxylic acid;
6-[2-(1-Aziridinyl)ethoxy]-3-pyridinmethanamin; 6-[2-(1-aziridinyl)ethoxy]-3-pyridinemethanamine;
6-[2-(1-Aziridinyl)ethoxy]-2-pyridincarboxylsäure; 6-[2-(1-Aziridinyl)ethoxy]-2-pyridinecarboxylic acid;
2-[2-(1-Aziridinyl)ethoxy]pyridin; 2-[2-(1-aziridinyl)ethoxy]pyridine;
2-Methyl-aziridin; 2-methyl-aziridine;
2-[1-(1-Aziridinylmethyl)propoxy]-pyridin; 2-[1-(1-aziridinylmethyl)propoxy]pyridine;
2-[2-(1-Aziridinyl)ethoxy]-4-Pyridinemethanamine; 2-[2-(1-aziridinyl)ethoxy]-4-pyridinemethanamine;
B) difunktionellen Aziridinen B) difunctional aziridines
N,N'-Hexamethylen-1,6-bis(1-aziridincarboxamid); N,N'-hexamethylene-1,6-bis(1-aziridinecarboxamide);
N,N'-(Methylendi-p-phenylen)bis(aziridin-1-carboxamid); N,N'-(Methylenedi-4,1-phenylene)bis[2-methyl-1-aziridincarboxamid];N,N'-(methylenedi-p-phenylene)bis(aziridine-1-carboxamide); N,N'-(Methylenedi-4,1-phenylene)bis[2-methyl-1-aziridinecarboxamide];
1-Aziridincarboxamid, N,N'-(3,3'-dimethyl[1, 1'-biphenyl]-4,4'-diyl)bis-;1-aziridinecarboxamide, N,N'-(3,3'-dimethyl[1,1'-biphenyl]-4,4'-diyl)bis-;
1-Aziridincarboxamid, N,N'-[1, 1'-biphenyl]-4,4'-diylbis-; 1-aziridinecarboxamide, N,N'-[1,1'-biphenyl]-4,4'-diylbis-;
1-Aziridincarboxamid, N,N'-(methylenedi-4,1-phenylene)bis-; 1-aziridinecarboxamide, N,N'-(methylenedi-4,1-phenylene)bis-;
1-Aziridincarboxamid, N,N'-(4-methyl-1,3-phenylene)bis-; 1-aziridinecarboxamide, N,N'-(4-methyl-1,3-phenylene)bis-;
1-Aziridincarboxamid, N,N'-(1,4-phenylenedi-2,1-ethanediyl)bis-; 1-aziridinecarboxamide, N,N'-(1,4-phenylenedi-2,1-ethanediyl)bis-;
1-Aziridincarboxamid, N,N'-1,4-phenylenebis-; 1-aziridinecarboxamide, N,N'-1,4-phenylenebis-;
N,N'-(Hexan-1,6-diyl)bis(2-methylaziridin-1-carboxamid); N,N'-(hexane-1,6-diyl)bis(2-methylaziridine-1-carboxamide);
N,N'-1,2-Ethandiylbis[1-aziridincarboxamid]; N,N'-1,2-ethanediylbis[1-aziridinecarboxamide];
N,N'-1,3-Propandiylbis[1-aziridincarboxamid]; N,N'-1,3-propanediylbis[1-aziridinecarboxamide];
N,N'-1,4-Butandiylbis[1-aziridincarboxamid]; N,N'-1,4-butanediylbis[1-aziridinecarboxamide];
N,N'-1,5-Pentandiylbis[1-aziridincarboxamid]; N,N'-1,5-pentanediylbis[1-aziridinecarboxamide];
N,N'-1,6-Hexandiylbis[1-aziridincarboxamid]; N,N'-1,6-hexanediylbis[1-aziridinecarboxamide];
N,N'-1,7-Heptandiylbis[1-aziridincarboxamid]; N,N'-1,7-heptanediylbis[1-aziridinecarboxamide];
N,N'-1,8-Octandiylbis[1-ziridincarboxamid]; N,N'-1,8-octanediylbis[1-ziridinecarboxamide];
N,N'-1,9-Nonandiylbis[1-aziridincarboxamid]; N,N'-1,9-nonanediylbis[1-aziridinecarboxamide];
N,N'-1,10-Decandiylbis[1-aziridincarboxamid]; N,N'-1,10-decanediylbis[1-aziridinecarboxamide];
1-Aziridincarboxamid, N,N'-(3-hydroxy-1,5-pentanediyl)bis-1-Aziridinecarboxamide, N,N'-(3-hydroxy-1,5-pentanediyl)bis-
1 -Aziridincarboxamid, N,N'-1,5-naphthalenediylbis-; 1 -aziridinecarboxamide, N,N'-1,5-naphthalenediylbis-;
1-Aziridincarboxamid, N,N'-(3,3'-dimethoxy[1, 1'-biphenyl]-4,4'-diyl)bis- 1-Aziridinecarboxamide, N,N'-(3,3'-dimethoxy[1,1'-biphenyl]-4,4'-diyl)bis-
1-Aziridincarboxamid, N,N'-(methyl-1,3-phenylen)bis-; 1-aziridinecarboxamide, N,N'-(methyl-1,3-phenylene)bis-;
1-Aziridincarboxamid, N,N'-[1, 1'-biphenyl]-4,4'-diylbis-; 1-aziridinecarboxamide, N,N'-[1,1'-biphenyl]-4,4'-diylbis-;
Poly(oxy-1,4-butanediyl), α-[[[3-[(1-aziridinylcarbonyl)amino]-4- methylphenyl]amino]carbonyl]-(ω -[[[[3-[(1-aziridinylcarbonyl)amino]-4- methylphenyl]amino]carbonyl]oxy]-; Poly(oxy-1,4-butanediyl), α-[[[3-[(1-aziridinylcarbonyl)amino]-4-methylphenyl]amino]carbonyl]-(ω -[[[[3-[(1-aziridinylcarbonyl )amino]-4-methylphenyl]amino]carbonyl]oxy]-;
N,N"-(Methylendi-4,1-phenylen)bis[N'-1-aziridinyl-harnstoff; N,N"-(methylenedi-4,1-phenylene)bis[N'-1-aziridinyl urea;
C) Trifunktionellen Aziridinen C) Trifunctional aziridines
Pentaerythritol tris[3-(1-aziridinyl)propionat]; pentaerythritol tris[3-(1-aziridinyl)propionate];
Trimethylolpropan-tris[3-(2-methylaziridin-1-yl)propionat]; trimethylolpropane tris[3-(2-methylaziridin-1-yl)propionate];
Trimethylolpropan-tris[3-(aziridin-1-yl)propionat]; trimethylolpropane tris[3-(aziridin-1-yl)propionate];
1 -Aziridinproprionsäure, 2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-1,3- propandiylester; 1-Aziridinproprionsäure, α-methyl-, 1, 1'-[2-[[3-(1-aziridinyl)-2-methyl-1-Aziridinepropionic acid, 2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propanediyl ester; 1-aziridinepropionic acid, α-methyl-, 1,1'-[2-[[3-(1-aziridinyl)-2-methyl-
1-oxopropoxy]methyl]-2-ethyl-1,3-propandiyl]ester; 1-oxopropoxy]methyl]-2-ethyl-1,3-propanediyl]ester;
1-Aziridinproprionsäure, 2-[[(1-aziridinylacetyl)oxy]methyl]-2-ethyl- 1,3-propandiylester; 1-aziridinepropionic acid, 2-[[(1-aziridinylacetyl)oxy]methyl]-2-ethyl-1,3-propanediyl ester;
1-Aziridinproprionsäure, 2-methyl-, 1, 1',1"-(2-ethyl-1,2,3-pro- pantriyl)ester; 1-aziridinepropionic acid, 2-methyl, 1,1',1"-(2-ethyl-1,2,3-propanetriyl) ester;
1 -Aziridincarboxamid, N,N',N"-(methylidynetri-4,1-phenylen)tris; 1 -aziridinecarboxamide, N,N',N''-(methylidynetri-4,1-phenylene)tris;
1 -Aziridincarboxamid, N,N'-[[[6-[(1-aziridinylcarbonyl)amino]hexyl]- imino]bis(carbonylimino-6,1-hexanediyl)]bis-; 1 -aziridinecarboxamide, N,N'-[[[6-[(1-aziridinylcarbonyl)amino]hexyl]imino]bis(carbonylimino-6,1-hexanediyl)]bis-;
1-Aziridinproprionsäure, 2-methyl-, 1, 1'-[2-ethyl-2-[[3-(2-methyl-1- aziridinyl)-1-oxopropoxy]methyl]-1,3-propandiyl]ester; 1-aziridinepropionic acid, 2-methyl, 1,1'-[2-ethyl-2-[[3-(2-methyl-1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propanediyl]ester;
1-Aziridinproprionsäure, 1, 1'-[2-[[3-(1-aziridinyl)-1-oxopropoxy]me- thyl]-2-ethyl-1,3-propandiyl]ester; 1-aziridinepropionic acid, 1,1'-[2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-2-ethyl-1,3-propanediyl]ester;
1-Aziridinproprionsäure, 1, 1'-[2-[[3-(1-aziridinyl)-1-oxopropoxy]me- thyl]-2-(hydroxymethyl)-1,3-propandiyl]ester; 1-aziridinepropionic acid, 1,1'-[2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-2-(hydroxymethyl)-1,3-propanediyl]ester;
Poly(oxy-1,2-ethanediyl), α,α',α"-1,2,3-propantriyltris[ ω-[[[[3-[(1- aziridinylcarbonyl)amino]-4-methylphenyl]amino]carbonyl]oxy]-; Aziri- dine, 1, 1',1"-(s-phenenyltricarbonyl)tris[2-methyl-; Poly(oxy-1,2-ethanediyl), α,α',α"-1,2,3-propanetriyltris[ω-[[[[3-[(1-aziridinylcarbonyl)amino]-4-methylphenyl]amino] carbonyl]oxy]-; aziridines, 1,1',1"-(s-phenenyltricarbonyl)tris[2-methyl-;
D) Tetrafunktionellen Aziridinen D) Tetrafunctional aziridines
Pentaerythritoltetrakis(β-aziridino)propionat; pentaerythritol tetrakis(β-aziridino)propionate;
1-Aziridinproprionsäure, 1, 1'-[2,2-bis[[3-(1-aziridinyl)-1-oxopropoxy]- methyl]-1,3-propandiyl]ester; 1-aziridinepropionic acid, 1,1'-[2,2-bis[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propanediyl]ester;
1-Aziridinproprionsäure, 2-methyl-, 1, 1'-[2,2-bis[[3-(2-methyl-1-aziridi- nyl)-1-oxopropoxy]methyl]-1,3-propandiyl]ester; 1-Aziridinepropionic acid, 2-methyl, 1,1'-[2,2-bis[[3-(2-methyl-1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propanediyl]ester ;
1 -Aziridinethanol, α,α'-[[2,2-bis[2-hydroxy-3-(2-methyl-1-aziridinyl)- propoxy]methyl]-1,3-propandiyl]bis(oxymethylene)]bis[2-methyl-;1 -Aziridineethanol, α,α'-[[2,2-bis[2-hydroxy-3-(2-methyl-1-aziridinyl)propoxy]methyl]-1,3-propanediyl]bis(oxymethylene)]bis [2-methyl-;
Ethanon, 2,2,,2",2'"-[[2,2,-bipyridine]-6,6,-diylbis(methyleneni- trilo)]tetrakis[1-(2-methyl-1-aziridinyl)-; Ethanone, 2,2 , ,2",2'"-[[2,2 , -bipyridine]-6,6 , -diylbis(methylenenitrilo)]tetrakis[1-(2-methyl-1-aziridinyl)- ;
1,5-Pentandion, 2-[bis[2-(2-methyl-1-aziridinyl)-2-oxoethyl]amino]-1,5- bis(2-methyl-1-aziridinyl)-; 1,5-pentanedione, 2-[bis[2-(2-methyl-1-aziridinyl)-2-oxoethyl]amino]-1,5-bis(2-methyl-1-aziridinyl)-;
Ethanon, 2,2',2",2",-(1,2-ethanediyldinitrilo)tetrakis[1-(2-methyl-1- aziridinyl)-; ethanone, 2,2',2",2" , -(1,2-ethanediyldinitrilo)tetrakis[1-(2-methyl-1-aziridinyl)-;
Methanon, 1, 1',1",l'"-(1,4,5,8-naphthalintetrayl)tetrakis[1-(2-methyl-methanone, 1,1',1",l'"-(1,4,5,8-naphthalenetetrayl)tetrakis[1-(2-methyl-
1-aziridinyl)-; 1 -Aziridinethanol, α,α'-[[2,2-bis[2-hydroxy-3-(2-methyl-1-aziridi- nyl)propoxy]methyl]-1,3-propandiyl]bis(oxymethylen)]bis[2-methyl-; 1-aziridinyl)-; 1-Aziridinethanol, α,α'-[[2,2-bis[2-hydroxy-3-(2-methyl-1-aziridinyl)propoxy]methyl]-1,3-propanediyl]bis(oxymethylene)] bis[2-methyl-;
E) Multifunktionellen Aziridinen E) Multifunctional aziridines
1 -Aziridinproprionsäure, 1, 1'-[2-[[3-[3-(1-aziridinyl)-1-oxopropoxy]-2,2- bis[[3-(1-aziridinyl)-1-oxopropoxy]methyl]propoxy]methyl]-2-[[3-(1- aziridinyl)-1-oxopropoxy]methyl]-1,3-propandiyl]ester; 1-Aziridinepropionic acid, 1,1'-[2-[[3-[3-(1-aziridinyl)-1-oxopropoxy]-2,2-bis[[3-(1-aziridinyl)-1-oxopropoxy]methyl ]propoxy]methyl]-2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propanediyl]ester;
1 -Aziridinproprionsäure, 2-methyl-, 1, 1'-[2-[[3-[3-(1-aziridinyl)-1-ox- opropoxy]-2-(hydroxymethyl)-2-[[3-(2-methyl-1-aziridinyl)-1-ox- opropoxy]methyl]propoxy]methyl]-2-[[3-(2-methyl-1-aziridinyl)-1-ox- opropoxy]methyl]-1,3-propandiyl]ester; 1-Aziridinepropionic acid, 2-methyl-, 1,1'-[2-[[3-[3-(1-aziridinyl)-1-oxopropoxy]-2-(hydroxymethyl)-2-[[3-( 2-methyl-1-aziridinyl)-1-ox-opropoxy]methyl]propoxy]methyl]-2-[[3-(2-methyl-1-aziridinyl)-1-ox-opropoxy]methyl]-1,3 -propanediyl]ester;
1-Aziridinproprionsäure, β,2-dimethyl-, benzylhexaylhexamethyl- enester; 1-aziridinepropionic acid, β,2-dimethyl, benzylhexaylhexamethylene ester;
1-Aziridinproprionsäure, 2-ethyl-β-methyl-, benzylhexaylhexakis(meth- ylen)ester; sowie Mischungen und Kombinationen aus den zuvor genannten Aziri- dinen. 1-aziridinepropionic acid, 2-ethyl-β-methyl, benzylhexaylhexakis(methylene) ester; and mixtures and combinations of the aforementioned aziridines.
3. Stabilisator-Zusammensetzung nach einem der vorhergehenden An- sprüche, dadurch gekennzeichnet, dass mindestens ein Aziridin ausge- wählt ist aus der Gruppe bestehend aus den nachfolgenden Verbin- dungen
Figure imgf000054_0001
3. Stabilizer composition according to one of the preceding claims, characterized in that at least one aziridine is selected from the group consisting of the following compounds
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000055_0001
4. Stabilisator-Zusammensetzung nach einem der vorhergehenden An- sprüche, dadurch gekennzeichnet, dass der mindestens eine Hydrotalcit ausgewählt ist aus der Gruppe bestehend aus Verbindungen der allge- meinen Formel 4. Stabilizer composition according to one of the preceding claims, characterized in that the at least one hydrotalcite is selected from the group consisting of compounds of the general formula
(M2+)1-x • (M3+)x • (OH)2 • (An-)x/n • m H2O wobei (M 2+ )1-x • (M 3+ )x • (OH) 2 • (A n- ) x/n • m H 2 O where
M2+ eines oder mehrere der Metalle aus der Gruppe Mg, Ca, Sr oder Zn, M 2+ one or more of the metals from the group Mg, Ca, Sr or Zn,
M3+ AI oder B, M 3+ AI or B,
A ein Anion mit der Valenz n, bevorzugt OH-, HCO3-, CH3COO-, C6H5COO-, CO3 2-, SO4 2-, HPO4 2-, n 1 oder 2 ist, A is an anion with the valence n, preferably OH-, HCO3-, CH3COO-, C 6 H 5 COO-, CO 3 2- , SO 4 2- , HPO 4 2- , n is 1 or 2,
0 < x < 0,5 ist, und m eine Zahl von 0 bis 20 ist, insbesondere die Hydrotalcite ausgewählt sind aus der Gruppe beste- hend aus Ca4AI2(OH)12 CO3 • 5 H2O, AI2O3 • 6 MgO • CO2 • 12 H2O, Mg4,5AI2(OH)13 • CO3 • 3,5 H2O, Mg6AI2(OH)16 • CO3 • 4 H2O, 4 MgO • AIO3 • CO2 • 9 H2O, 4 MgO • AI2O3 • CO2 • 6 H2O, ZnO • 3 MgO • AI2O3 • CO2 • 8-9 H2O und ZnO • 3 MgO • AI2O3 • CO2 • 5-6 H2O. 0<x<0.5, and m is a number from 0 to 20, in particular the hydrotalcites are selected from the group consisting of Ca 4 AI 2 (OH) 12 CO 3 • 5 H 2 O, Al 2 O 3 • 6 MgO • CO 2 • 12 H 2 O, Mg 4.5 AI 2 (OH) 13 • CO 3 • 3.5 H 2 O, Mg 6 AI 2 (OH) 16 • CO 3 • 4 H 2 O, 4 MgO • AIO 3 • CO 2 • 9 H 2 O, 4 MgO • Al 2 O 3 • CO 2 • 6 H 2 O, ZnO • 3 MgO • Al 2 O 3 • CO 2 • 8-9 H 2 O and ZnO • 3 MgO • Al 2 O 3 • CO 2 • 5-6 H 2 O.
5. Stabilisator-Zusammensetzung nach einem der vorhergehenden An- sprüche, dadurch gekennzeichnet, dass der mindestens eine Dawsonit ausgewählt ist aus der Gruppe bestehend aus Verbindungen der allge- meinen Formel 5. Stabilizer composition according to one of the preceding claims, characterized in that the at least one dawsonite is selected from the group consisting of compounds of the general formula
{(M2O)m • ( AI2O3) • Zo • p H2O} wobei {( M2O ) m •( AI2O3 )• Zo • pH2O } where
M ein Element, ausgewählt aus der Gruppe bestehend aus H, Li, Na, K, Mg1/2, Ca1/2, Sr1/2, Zn1/2; M an element selected from the group consisting of H, Li, Na, K, Mg 1/2 , Ca 1/2 , Sr 1/2 , Zn 1/2 ;
Z ein Substituent, ausgewählt aus der Gruppe bestehend aus CO2, SO2, (Cl2O7)1/2, B4O6, S2O2 (Thiosulfat) und/oder C2O2 (Oxalat); m wenn M Mg1/2, Ca1/2, ist, eine Zahl zwischen 1 und 2, in allen an- deren Fällen eine Zahl zwischen 1 und 3; n eine Zahl zwischen 1 und 4; o eine Zahl zwischen 2 und 4; und p eine Zahl zwischen 0 und 30 insbesondere der mindestens eine Dawsonit ausgewählt ist aus derZ is a substituent selected from the group consisting of CO 2 , SO 2 , (Cl 2 O 7 ) 1/2 , B 4 O 6 , S 2 O 2 (thiosulfate) and/or C 2 O 2 (oxalate); m if M is Mg 1/2 , Ca 1/2 , a number between 1 and 2, in all other cases a number between 1 and 3; n is a number between 1 and 4; o a number between 2 and 4; and p is a number between 0 and 30, in particular the at least one dawsonite is selected from the
Gruppe bestehend aus group consisting of
Kaliumalumocarbonat {(K20) •( AI2O3)·(CO2)2 • 2 H2O}, Natriumalumothio- sulfat {(Na20)·( AI2O3)·( S2O2)2·2 H2O}, KaliumalumosulfitPotassium aluminocarbonate {(K 20 )•( AI 2 O 3 )•(CO 2 ) 2 • 2 H 2 O}, sodium aluminothiosulfate {(Na 2 O)•( AI 2 O 3 )•( S 2 O 2 ) 2 •2 H 2 O}, potassium alumosulfite
{(K20) •( AI2O3)·(CO2)2 • 2 H2}O, Calciumalumooxalat {(CaO)-(Al2O3)-(C2O2)2-5 H2O}, Magnesiumalumotetraborat {(MgO)-(Al2O3)-(B4O6)2-5 H2O}, Natri- umalumodihydroxycarbonat, Kaliumalumodihydroxycarbonat sowie natürlich vorkommende Alkalialumocarbonat-Mineralien, wie z.B. Indi- girit, Tunisit, Alumohydrocalcit und Strontiodresserit. {(K 20 ) •( AI 2 O 3 )·(CO 2 ) 2 • 2 H 2 }O, calcium alumooxalate {(CaO)-(Al2O3)-(C 2 O2)2-5 H2O}, magnesium alumotetraborate {(MgO )-(Al2O3)-(B4O6)2-5 H2O}, sodium alumodihydroxycarbonate, potassium alumodihydroxycarbonate and naturally occurring alkali aluminocarbonate minerals such as indigirite, tunisit, alumohydrocalcite and strontiodresserite.
6. Stabilisator-Zusammensetzung nach einem der vorhergehenden An- sprüche, dadurch gekennzeichnet, dass der mindestens eine Zeolith ausgewählt ist aus der Gruppe bestehend aus Verbindungen der allge- meinen Formel 6. Stabilizer composition according to one of the preceding claims, characterized in that the at least one zeolite is selected from the group consisting of compounds of the general formula
Mx/n[(AIO2]x(SiO2)y w H20 wobei n die Ladung des Kations M; M x/n [(AIO 2 ] x (SiO 2 ) y w H20 where n is the charge of the cation M;
M ein Element der ersten oder zweiten Hauptgruppe, insbesondere Li, Na, K, Mg, Ca, Sr oder Ba; y:x einen Wert von 0,8 bis 15, bevorzugt von 0,8 bis 1,2, und w eine Zahl von 0 bis 300, bevorzugt von 0,5 bis 5 ist, insbesondere der mindestens eine Zeolith ausgewählt ist aus der Gruppe bestehend aus M an element of the first or second main group, in particular Li, Na, K, Mg, Ca, Sr or Ba; y:x has a value from 0.8 to 15, preferably from 0.8 to 1.2, and w is a number from 0 to 300, preferably from 0.5 to 5, in particular the at least one zeolite is selected from the group consisting of
Natriumalumosilikaten der Formeln Na12Al12Si12O48.·27 H2O [Zeolith A], Na6Al6Si5O24 • 2 NaX • 7,5 H2O (X= OH, Halogen, CIO4 [Sodalith]); Na6Al6Si30O72 • 24 H2O; Na8Al8Si40O95 · 24 H2O; Na16Ali6Si24O80 · 16 H;2O Na16Ali6Si32O96 · 16 H2O; Na56AI56Si136O384 • 250 H2O [Zeolith Y], Na86Al86Si106O384 • 264 H2O [Zeolith X]; K9Al9Si27O72 · 22 H2O [Zeolith L]; sowie Zeolithe bei denen die Na-Atome der zuvor genannten Zeolithe teilweise bzw. vollständig durch Li-, K-, Mg-, Ca-, Sr- oder Zn-Atome aus- getauscht sind, wie insbesondere (Na,K)10Al10Si22O64 • 20 H2O, Ca4,5Na3[(AIO2)12(SiO2)12 • 30 H2O und K9Na3[(AIO2)12SiO2)12] • 27 H2O;Sodium aluminosilicates of the formulas Na 12 Al 12 Si 12 O 48 .27 H 2 O [zeolite A], Na 6 Al 6 Si 5 O 24 • 2 NaX • 7.5 H 2 O (X=OH, halogen, CIO 4 [ sodalite]); Na 6 Al 6 Si 30 O 72 • 24 H 2 O; Na 8 Al 8 Si 40 O 95 · 24 H 2 O; Na 16 Ali 6 Si 24 O 80 x 16 H; 2 O Na 16 Ali 6 Si 32 O 96 · 16 H 2 O; Na 56 Al 56 Si 136 O 384 • 250 H 2 O [zeolite Y], Na 86 Al 86 Si 106 O 384 • 264 H 2 O [zeolite X]; K 9 Al 9 Si 27 O 72 · 22 H 2 O [zeolite L]; and zeolites in which the Na atoms of the aforementioned zeolites are partially or completely replaced by Li, K, Mg, Ca, Sr or Zn atoms, such as in particular (Na,K) 10 Al 10 Si 22 O 64 • 20 H 2 O, Ca 4 .5 Na 3 [(AIO 2 ) 12 (SiO 2 ) 12 • 30 H 2 O and K 9 Na 3 [(AIO 2 ) 12 SiO 2 ) 12 ] • 27 H2O ;
7. Stabilisator-Zusammensetzung nach einem der vorhergehenden An- sprüche, dadurch gekennzeichnet, dass der mindestens eine Hydrotal- cit, Zeolith, Dawsonite oder die Mischung hiervon bevorzugt wasserfrei sind. 7. Stabilizer composition according to one of the preceding claims, characterized in that the at least one hydrotalcite, zeolite, dawsonite or the mixture thereof is preferably anhydrous.
8. Stabilisator-Zusammensetzung nach einem der vorhergehenden An- sprüche, dadurch gekennzeichnet, dass das Gewichtsverhältnis der Ge- samtheit der Aziridin zur Gesamtheit des mindestens einen Hydrotalci- tes, Dawsoniten und/oder Zeoliths 20:1 bis 1:20, bevorzugt von 10:1 bis 1:10, besonders bevorzugt von 5:1 bis 1:5 beträgt. 8. Stabilizer composition according to one of the preceding claims, characterized in that the weight ratio of all of the aziridine to all of the at least one hydrotalcite, dawsonite and/or zeolite is 20:1 to 1:20, preferably from 10 :1 to 1:10, particularly preferably from 5:1 to 1:5.
9. Verwendung einer Stabilisator-Zusammensetzung nach einem der An- sprüche 1 bis 8 zur Stabilisierung von Kondensationspolymeren gegen hydrolytischen Abbau. 9. Use of a stabilizer composition according to any one of claims 1 to 8 for stabilizing condensation polymers against hydrolytic degradation.
10. Verfahren zur Stabilisierung von Kondensationspolymeren gegen hyd- rolytischen Abbau, bei dem dem Kondensationspolymer eine Stabilisa- tor-Zusammensetzung nach einem der Ansprüche 1 bis 8 zugemischt oder mit dieser geblendet wird. 10. A process for stabilizing condensation polymers against hydrolytic degradation, in which a stabilizer composition as claimed in any of claims 1 to 8 is admixed to the condensation polymer or blended with it.
11. Verwendung oder Verfahren nach einem der Ansprüche 9 oder 10, dadurch gekennzeichnet, dass die Stabilisator-Zusammensetzung in ei- nem Gewichtsverhältnis von 0,01 bis 10 Gew.-%, bevorzugt von 0,05 bis 5 Gew.-%, besonders bevorzugt von 0,1 bis 3 % Gew.-% bezogen auf das Polykondensationspolymere verwendet bzw. zugemischt wird. 11. Use or method according to any one of claims 9 or 10, characterized in that the stabilizer composition is present in a weight ratio of from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, in particular preferably from 0.1 to 3% by weight, based on the polycondensation polymer, is used or mixed in.
12. Verwendung oder Verfahren nach einem der Ansprüche 9 bis 11, dadurch gekennzeichnet, dass das Polykondensationspolymere ausge- wählt ist aus der Gruppe bestehend aus a) Polyamiden, wie z.B. Polyamid-6, 6.6, 6.9, 6.10, 4.6, 4.10, 6.12, 10.10, 10.12, 12.12, Polyamid 4, Polyamid, 7, Polyamid 8, Poly- amid 9, Polyamid 11, Polyamid 12 sowie (teil-)aromatische Poly- amide wie z.B. Polyphthalamide, z.B. hergestellt aus Terephthal- säure und/oder Isophthalsäure und aliphatischen Diaminen wie z.B. Hexamethylendiamin oder m-Xylylendiamin oder aus aliphati- schen Dicarbonsäuren wie z.B. Adipinsäure oder Sebazin-säure und aromatischen Diaminen wie z.B. 1,4- oder 1,3- Diaminobenzol, bezeichnet z.B. als Polyamid 6T, Polyamid 9T, Polyamid 61, Poly- amid-6-3-T, Blends von unterschiedlichen Polyamiden wie z.B. PA- 6 und PA 6.6, PA6T und PA6I, PA-6.6 und PA6T bzw. Blends von Polyamiden und Polyolefinen wie z.B. PA/PP oder PA/PE, b) Polyestern aus aliphatischen oder aromatischen Dicarbonsäuren und Diolen oder aus Hydroxy-Carbonsäuren, insbesondere alipha- tischen Polyestern, wie z.B. Polyethylenterephthalat (PET), Polyb- utylenterephthalat (PBT), Polytrimethylenterephthalat (PTT), Po- lypropylenterephthalat (PPT), Polyethylennaphthylat (PEN), Poly- 1,4-dimethylol-cyclo-hexanterephthalat, Polyhydroxybenzoat, Po- lyhydroxynaphthalat, Polymilchsäure (PLA), Polyhydroxybutyrat (PHB), Polyhydroxyvalerat (PHV), Polybutylensuccinat (PBS), Polyb- utylensuccinat-adipat (PBSA), Polyethylensuccinat, Polytetrame- thylensuccinat, Polycaprolacton, c) Polycarbonaten, Polyestercarbonaten, sowie Blends wie z.B. 12. Use or method according to any one of claims 9 to 11, characterized in that the polycondensation polymer is selected from the group consisting of a) polyamides, such as polyamide-6, 6.6, 6.9, 6.10, 4.6, 4.10, 6.12, 10.10, 10.12, 12.12, polyamide 4, polyamide 7, polyamide 8, polyamide 9, polyamide 11, polyamide 12 and (partly) aromatic polyamides such as polyphthalamides, for example produced from terephthalic acid and/or isophthalic acid and aliphatic diamines such as hexamethylenediamine or m-xylylenediamine or from aliphatic dicarboxylic acids such as adipic acid or sebacic acid and aromatic diamines such as 1,4- or 1,3-diaminobenzene, referred to for example as polyamide 6T, polyamide 9T, polyamide 61, Polyamide-6-3-T, blends of different polyamides such as PA-6 and PA 6.6, PA6T and PA6I, PA-6.6 and PA6T or blends of polyamides and polyolefins such as PA/PP or PA/PE, b ) Polyesters from aliphatic or aromatic dicarboxylic acids and diols or from Hydr oxy-carboxylic acids, in particular aliphatic polyesters, such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polypropylene terephthalate (PPT), polyethylene naphthylate (PEN), poly- 1,4-dimethylol cyclohexane terephthalate, polyhydroxybenzoate, polyhydroxynaphthalate, polylactic acid (PLA), polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polyethylene succinate, polytetramethylene succinate , Polycaprolactone, c) polycarbonates, polyester carbonates, and blends such as
PC/ABS, PC/PBT, PC/PET/PBT, PC/PA, d) sowie Mischungen, Kombinationen oder Blends aus zwei oder mehr der zuvor genannten Polymeren. PC/ABS, PC/PBT, PC/PET/PBT, PC/PA, d) and mixtures, combinations or blends of two or more of the aforementioned polymers.
13. Hydrolysestabilisierte Zusammensetzung, enthaltend oder bestehend aus mindestens einem Kondensationspolymer sowie einer Stabilisator-Zusammensetzung nach einem der Ansprüche 1 bis 8. 13. Hydrolysis-stabilized composition containing or consisting of at least one condensation polymer and a stabilizer composition according to any one of claims 1 to 8.
14. Hydrolysestabilisierte Zusammensetzung nach vorhergehendem An- spruch, dadurch gekennzeichnet, dass die Stabilisator-Zusammenset- zung in einem Gewichtsverhältnis von 0,01 bis 10 Gew.-%, bevorzugt von 0,05 bis 5 Gew.-%, besonders bevorzugt von 0,1 bis 3 % Gew.-% bezogen auf das Polykondensationspolymere enthalten ist. 14. Hydrolysis-stabilized composition according to the preceding claim, characterized in that the stabilizer composition is present in a weight ratio of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, particularly preferably 0 1 to 3% by weight based on the polycondensation polymer.
15. Hydrolysestabilisierte Zusammensetzung nach einem der beiden vor- hergehenden Ansprüche, dadurch gekennzeichnet, dass mindestens ein Zusatzstoff, ausgewählt aus der Gruppe bestehend aus sekundären Antioxidantien, UV-Absorber, der Lichtstabilisatoren, der Metalldesak- tivatoren, der Füllstoffdesaktivatoren, der Antiozonantien, Nukleie- rungsmittel, Antinukleierungsmittel, Schlagzähigkeitsverbesserer, Weichmacher, Gleitmittel, Rheologiemodifikatoren, Thixotropiemittel, Kettenverlängerer, Verarbeitungshilfsmittel, Entformungshilfsmittel, Flammschutzmittel, Pigmente, Farbstoffe, optische Aufheller, antimik- robielle Wirkstoffe, Antistatika, Slipmittel, Antiblockmittel, Kopplungs- mittel, Vernetzungsmittel, Antivernetzungsmittel, Hydrophilisierungs- mittel, Hydrophobierungsmittel, Hydrolysestabilisatoren, Haftvermitt- ler, Dispergiermittel, Kompatibilisatoren, Sauerstofffänger, Säurefän- ger, Treibmittel, Abbau-Additive, Entschäumungshilfsmittel, Geruchs- fänger, Markierungsmittel, Antifoggingmittel, Füllstoffe und Verstär- kungsstoffe enthalten ist. 15. Hydrolysis-stabilized composition according to one of the two preceding claims, characterized in that at least one additive selected from the group consisting of secondary antioxidants, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nuclei agents, antinucleating agents, impact modifiers, plasticizers, lubricants, rheology modifiers, thixotropic agents, chain extenders, processing aids, mold release agents, flame retardants, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anticrosslinking agents, hydrophilic agents, water repellents, hydrolysis stabilizers, adhesion promoters ler, dispersing agents, compatibilizers, oxygen scavengers, acid scavengers, blowing agents, degradation additives, defoaming aids, odor scavengers, marking agents, antifogging agents, fillers and reinforcing materials.
16. Hydolysestabiliserte Zusammensetzung nach einem der Ansprüche 13 bis 15, dadurch gekennzeichnet, dass das mindestens eine Kondensati- onspolymer ausgewählt ist aus der Gruppe bestehend aus aliphati- schen Polyestern. 16. Hydrolysis-stabilized composition according to any one of claims 13 to 15, characterized in that the at least one condensation polymer is selected from the group consisting of aliphatic polyesters.
17. Formteil oder Formkörper, herstellbar aus einer hydrolysestabilisierten Zusammensetzungen nach einem der Ansprüche 13 bis 16, insbeson- dere Folien oder Filme, Schäume, Fasern, Kabel und Rohre, Profile, Hohlkörper, Bändchen, Membranen, wie z.B. Geomembranen, oder Klebstoffe, die über Extrusion, Spritzguss, Blasformen, Kalandrieren, Pressverfahren, Spinnprozesse, Rotomoulding hergestellt werden z.B. für die Elektro- und Elektronikindustrie, Bauindustrie, Transportindust- rie (Auto, Flugzeug, Schiff, Bahn), für medizinische Anwendungen, für Haushalts- und Elektrogeräte, Fahrzeugteile, Konsumartikel, Verpa- ckungen, Möbel, Textilien. 17. Shaped part or shaped body, producible from a hydrolysis-stabilized composition according to any one of claims 13 to 16, in particular foils or films, foams, fibers, cables and pipes, profiles, hollow bodies, ribbons, membranes, such as geomembranes, or adhesives that via extrusion, injection moulding, blow moulding, calendering, pressing processes, spinning processes, rotomoulding, e.g. for the electrical and electronics industry, construction industry, transport industry (car, aircraft, ship, train), for medical applications, for household and electrical appliances, vehicle parts , consumer goods, packaging, furniture, textiles.
PCT/EP2022/057056 2021-03-17 2022-03-17 Stabilizer composition, use of the stabilizer composition, method for stabilizing condensation polymers against hydrolytic degradation, and hydrolysis-stabilized composition and molding or molded part consisting thereof WO2022195041A1 (en)

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